CN1723171B - Method for producing tubular carbon molecules - Google Patents

Abstract

A method of manufacturing tubular carbon molecules capable of arranging carbon nanotubes at finer intervals and in a regular pattern. The catalyst is arranged on a substrate (10) composed of a semiconductor, such as silicon (Si), by melting based on a modulated heat distribution (11), said substrate containing iron as catalyst. The thermal profile (11) is formed by diffracting an energy beam (12) with, for example, a diffraction grating (12). The method of distributing the catalyst comprises, for example, depositing iron in a planar or convex form in the positions corresponding to said thermal profile (11), or also transferring it to another substrate using its original form. Growing carbon nanotubes using the distributed catalyst. The grown nanotubes can be used in recording devices, field electron emission devices, or FEDs.

Description

Method for making tubular carbon molecules

technical field

The present invention relates to a method for producing tubular carbon molecules capable of arranging tubular carbon molecules (such as carbon nanotubes) in a fine pattern, and to obtaining tubular carbon molecules by the above method. Furthermore, the present invention relates to a method of manufacturing a recording device using the tubular carbon molecule and a recording device using the tubular carbon molecule, and also to a method of manufacturing a field electron emission device including a cathode using the tubular carbon molecule and the The field electron emission device obtained by the above method also relates to a method of manufacturing a display unit using the field electron emission device and a display unit using the field electron emission device.

Background technique

In recent years, nanotechnology has achieved remarkable development, especially the molecular structure (such as carbon nanotube) is a stable material with good properties (such as high thermal conductivity, high electrical conductivity and high mechanical strength), so it is expected that the molecular The structures can be used in a wider range of applications, such as transistors, memory and field electron emission devices.

For example, as one application of carbon nanotubes, it is known that said carbon nanotubes can be suitably used to obtain cold cathode field electron emission (hereinafter referred to as "field electron emission") (see, for example, Yahachi Saito, Journal of The Surface Science Society of Japan, 1998, Vol. 19, No. 10, pp. 680-686). The field electron emission is a phenomenon that, when an electric field greater than a predetermined threshold value is applied to a metal or semiconductor placed in a vacuum, electrons pass through an energy barrier near the surface of the metal or semiconductor by quantum tunneling, so that even at room temperature Electrons can also be ejected into vacuum.

FEDs (Field Emission Displays), which display images using the principle of field electron emission, have features such as high intensity, low power consumption, and low profile, and the FEDs have been developed as replacements for conventional cathode ray tubes (CRTs) Display unit (see, for example, Japanese Unexamined Patent Application Publications 2002-203473 and 2000-67736). As a typical structure of an FED, a cathode plate (in which a cathode for emitting electrons is formed) and an anode plate (in which an anode is coated with a fluorescent layer to emit light by collision excitation of emitted electrons) are combined into a unit facing each other. The interior is in a high vacuum state. However, in this structure, it is difficult to arrange the cathode plate and the anode plate at a close distance, so a high voltage must be applied between the cathode plate and the anode plate. Therefore, an extraction electrode (gate electrode) is distributed between the cathode plate and the anode plate to bring the cathode and the extraction electrode closer, thereby applying a low voltage between the electrodes to cause field electron emission.

Fig. 75 depicts a cross-sectional view of the structure of an example of such a conventional FED. In this example, as a cathode structure, a so-called Spindt (from a person's name) type structure of a conical shape is described (see, for example, C.A. Spindt and three others, Journal of Applied Physics, (U.S.), 1976, Vol. 47, pp. 5248-5263 and Japanese Unexamined Patent Application Publication No. 2002-203473).

The FED includes a cathode plate 1100 and an anode plate 1200 facing the cathode plate 1100 . The cathode plate 1100 includes a base material 1120 and an extraction electrode 1140 facing the cathode electrode 1110 with an insulating film 1130 therebetween. The cathode electrode 1110 is formed on the base material 1120 . A plurality of cathode electrodes 1110 and a plurality of extraction electrodes 1140 are formed, and each extraction electrode 1140 is distributed at right angles to the cathode electrodes 1110 . On the substrate 1120, many cathodes 1150 are distributed on the surface of the cathode 1110 facing the extraction electrode.

In each extraction electrode 1140 , many small hole portions 1160 are distributed corresponding to each cathode 1150 , and the size of the small hole portions 1160 is the same as that of electron e ⁻ , so that electrons emitted by the cathode 1150 can pass through. Also, a scan driver (not shown) that cyclically applies a scan voltage to each of the extraction electrodes 1140 is electrically connected to each of the extraction electrodes 1140 . On the other hand, a data driver (not shown) selectively applying a voltage to each cathode electrode 1110 according to an image signal is electrically connected to each cathode electrode 1110 .

Each cathode 1150 is distributed in a matrix corresponding to a certain position, wherein the extraction electrodes 1140 and cathode electrodes 1110 cross each other, and the lower surface of each cathode 1150 is electrically connected to the corresponding cathode electrode 1110 . The cathode 1150 emits electrons from its tip portion according to a tunnel effect by selectively applying a predetermined electric field. Furthermore, in a typical FED, a predetermined number (for example, 1000) of cathode 1150 groups correspond to 1 pixel.

The anode plate 1200 includes an optically transparent transparent substrate 1210 and an anode electrode 1220 made of glass material, and the anode electrode 1220 is distributed on the side of the transparent substrate 1210 facing the cathode plate 1100 On the surface. A plurality of anode electrodes 1220 corresponding to the cathode electrodes 1110 are formed. Moreover, a fluorescent substance capable of emitting light according to incoming electrons e ⁻ is applied to the surface of the anode electrode 1220 closer to the transparent substrate 1210 to form a fluorescent film 1230 . Also, the anode electrode 1220 may be made of a transparent conductive material such as ITO (Indium-Tin Oxide), and the fluorescent film 1230 may be formed on the surface of the anode electrode 1220 closer to the cathode plate 1100 side.

In the FED having this structure, when a voltage is selectively applied between the extraction electrode 1140 and the cathode electrode 1110, field electron emission occurs at the intersection of the extraction electrode 1140 and the cathode electrode 1110. In the cathode 1150 , electrons e ⁻ are emitted to the anode 1220 . Electrons e ⁻ emitted from the cathode 1150 pass through pores (not shown) in the anode electrode 1220 and collide with the phosphorescent film 1230, thereby causing the phosphor to emit light. The desired image is displayed by the luminescence of the fluorescent substance.

In FED, field electron emission is induced by a lower voltage, so various attempts have been made to locally increase the electric field intensity by tipping the top of the cathode, and carbon nanotubes have been gradually used in these attempts (see, for example, Yahachi Saito, Journal of The Surface Science Society of Japan, Vol. 19, No. 10, pp. 680-686). For example, an FED using a single-walled carbon nanotube formed as a cathode at the tip of a silicon (Si) wafer by a thermal CVD (Chemical Vapor Deposition) method has been proposed. (See, eg, Abstracts of the 49th Enlarged Meeting of the Japan Society of Applied Physics and Related Societies, 29p-k-7). Moreover, it has been reported that after forming a silicon emitter by a conventional method, forming a thin film made of a metal catalyst for carbon nanotube formation, and removing the catalyst on the gate electrode by an etch-back method, the carbon nanotube Only the tip portion of the emitter was grown by the thermal CVD method (see Nikkan Kogyo shimbun, "Electron emission from CNT field emitter at low voltage of 4V", April 11, 2002).

In this application field, the carbon nanotubes are not used alone, but a carbon nanotube structure including many carbon nanotubes is used. Conventional semiconductor techniques such as photolithography and CVD (Chemical Vapor Deposition) can be used as a method of manufacturing the carbon nanotube structure. Also, a technique of introducing foreign materials into carbon nanotubes has been disclosed (see, for example, Masafumi Ata and three others, Japanese Journal of Applied Physics (Jpn.J.Appl.Phys.), 1995, Vol. 34, pp. 4207-4212 and Masafumi Ata and two others, Advanced Materials, (Germany), 1995, Vol. 7, pp. 286-289).

Also, as other technologies related to the present invention, they are a magnetic recording device and a magnetic recording apparatus. Their principle is that a magnetic material is magnetized and, by coercivity, the direction of magnetization corresponds to 1 or 0, or an analogue of a signal that records the degree of magnetization of said magnetic material when it is magnetized. In this case, both in-plane magnetization parallel to the recording surface and perpendicular magnetization perpendicular to the recording surface have been practically used. In recent years, it is necessary to further increase the recording density. Generally, the recording density is generally increased by reducing the magnetization length. As far as the latest knowledge known to the inventors is concerned, there is no disclosure of applying carbon nanotubes to the magnetic recording technology. try.

In order to obtain FED etc. using carbon nanotubes, there must be a technique which can form a fine pattern of catalysts made of transition metals or the like so that carbon nanotubes are regularly arranged in a fine arrangement pattern. Often, however, photolithography is the only technique that can achieve mass production to some extent. Photolithography is a major technique suitable for forming two-dimensional structures, so photolithography is not suitable for forming three-dimensional structures, such as carbon nanotube structures.

Also, in order to form fine patterns of metal catalysts by photolithography, there is currently no method to lower the wavelength of energy beams, and it is difficult to further lower the wavelength in the prior art. Therefore, in the case of forming a pattern of a transition metal or the like by photolithography, the size of the transition metal pattern and the interval between the patterns is determined by the wavelength of the energy beam, and in the prior art, the size does not It cannot be reduced to 0.05 micron (50 nanometers) or less, and the interval (pitch) between patterns cannot be reduced to 100 nanometers or less. In other words, the conventional technique has a problem of being unable to form finer patterns of metal catalysts and the like.

Also, in a cathode using conventional carbon nanotubes, many carbon nanotubes are closely distributed, so there is a problem that the electric field intensity on the surface of each carbon nanotube is significantly lowered. Therefore, in order to increase the electric field intensity on the surface of the carbon nanotube, it is necessary to apply a high voltage between the cathode electrode and the extraction electrode or the anode electrode, so it is difficult to lower the voltage.

In addition, the shapes and growth directions of many carbon nanotubes constituting the cathode are non-uniform, so the number of emitted electrons is also non-uniform, resulting in a problem of variation in luminance.

Contents of the invention

As described above, the first object of the present invention is to provide a method for producing tubular carbon molecules which can regularly arrange carbon nanotubes at finer intervals.

A second object of the present invention is to provide tubular carbon molecules regularly arranged at finer intervals, which are suitable for use in the manufacture of FEDs, recording devices, and the like.

A third object of the present invention is to provide a method of manufacturing a recording device and a recording device capable of further increasing the recording density by using carbon molecules regularly arranged at finer intervals.

A fourth object of the present invention is to provide a method for manufacturing field electron emission and a field electron emission device obtained by said method, said method enabling mass production of field electron emission devices including a cathode in which , carbon nanotubes are regularly arranged at finer intervals.

A fifth object of the present invention is to provide a method of manufacturing a display unit capable of mass-producing finely spaced display units by using field-induced electrons including a cathode, and a display unit obtained by the method. In the cathode, carbon nanotubes are regularly arranged at finer intervals to clearly display clearer images.

The method for producing tubular carbon molecules of the present invention includes: a catalyst alignment step of distributing metals having a catalytic function for tubular carbon molecules by melting by modulating heat distribution; and a growing step of growing tubular carbon molecules.

The tubular carbon molecule of the present invention is formed by arranging metal having catalytic function for tubular carbon molecule by melting and growing tubular carbon molecule using the metal having catalytic function by modulating heat distribution.

The method for manufacturing a recording device of the present invention includes: a catalyst alignment step of aligning metals having a catalytic function for tubular carbon molecules by melting, said melting being achieved by modulating heat distribution; and a growing step of growing tubular carbon molecules; A homogenization step of forming the tip of the tubular carbon molecule in a predetermined plane and forming the tip into an open tip; an insertion step of inserting the magnetic material into at least the tip of the tubular carbon molecule from the open tip A tip section.

The method for manufacturing a field electron emission device of the present invention includes: a catalyst arrangement step of arranging metals having a catalytic function for tubular carbon molecules on a substrate by modulating heat distribution; and a cathode growth step of forming a cathode by growing tubular carbon molecules.

The field electron emission device of the present invention includes a cathode including tubular carbon molecules grown using a metal having a catalytic function for the tubular carbon molecules, the tubular carbon molecules being arranged on a substrate by melting by This is achieved by modulating the heat distribution.

In the method of manufacturing a display unit of the present invention, the display unit includes a field electron emission device and a light emitting part based on electron collision light emission, the electrons are emitted from the field electron emission device and form the field electron emission The steps of the device include: a catalyst arrangement step, which arranges a metal having a catalytic function for tubular carbon molecules on a substrate by melting, said melting being achieved by modulating the heat distribution; and a cathode growth step, which forms a cathode by growing tubular carbon molecules .

The display unit of the present invention includes a field electron emission device and a light emitting part based on electron collision light emission, the electrons are emitted from the field electron emission part, the field electron emission device includes a cathode, and the cathode includes a pair of tubular Carbon molecules Tubular carbon molecules grown from metals with catalytic functions arranged on a substrate by melting by modulating the heat distribution.

In the method for producing tubular carbon molecules of the present invention and in the tubular carbon molecules of the present invention, a pattern composed of a metal having a catalytic function for the formation of tubular carbon molecules is formed by melting by modulating the heat distribution . After that, tubular carbon molecules are formed by using the formed pattern.

In the method of manufacturing a recording device of the present invention, the metal having a catalytic function for forming tubular carbon molecules is arranged in a desired pattern by melting by modulating heat distribution. After that, tubular carbon molecules are grown by using a metal having a catalytic function, and the tip of the tubular molecule is formed in a predetermined plane, and the tip is formed into an open tip. Then, a magnetic material is inserted into the tip portion of the tubular carbon molecule from the open tip to form a magnetic layer.

In the recording device of the present invention, the magnetic layer inserted into each tubular carbon molecule is separated from the magnetic layers in other adjacent tubular carbon molecules, so that information can be accurately read and written on the magnetic layer in each tubular carbon molecule.

In the method of manufacturing a field electron emission device of the present invention, in the field electron emission device of the present invention, in the method of manufacturing a display unit of the present invention, and in the display unit of the present invention, the tubular carbon molecule will be catalyzed by melting The functional metal is distributed on the substrate and the melting is achieved by modulating the heat distribution. Afterwards, tubular carbon molecules are grown to form the cathode.

Brief description of the drawings

Fig. 1 is a schematic diagram describing a first example of the present invention, i.e. a melting step in a method for manufacturing carbon nanotubes;

FIG. 2 is a schematic diagram describing a step (deposition step) subsequent to the step shown in FIG. 1;

Fig. 3 is a schematic diagram describing a step (growth step) subsequent to the step shown in Fig. 2;

4A and 4B are schematic diagrams describing the second example of the present invention, i.e. a highly homogenized step in the method for manufacturing carbon nanotubes;

5A and 5B are diagrams illustrating a fourth example of the present invention, ie, an insertion step in a method of manufacturing a recording device.

Figure 6 is a schematic diagram of an example of the recording device shown in Figures 5A and 5B being in a recording state;

Fig. 7 is a schematic diagram describing the melting step in the improved method 1 of the present invention, that is, the method for manufacturing carbon nanotubes;

8 is a schematic diagram of an example of forming a heat distribution on the surface of a substrate shown in FIG. 7;

Figure 9 is a plan view of another example of the heat distribution shown in Figure 7;

Fig. 10 is a schematic diagram describing a step (deposition step) subsequent to the step shown in Fig. 7;

Fig. 11 is a partially enlarged plan view of the substrate surface shown in Fig. 10;

Fig. 12 is a schematic diagram describing a step (growing step) subsequent to the step shown in Fig. 10;

Figure 13 is a partially enlarged plan view of the substrate surface shown, wherein the deposition step is performed after forming the thermal profile shown in Figure 9;

Fig. 14 is a schematic diagram describing the deposition steps in the improved method 2 of the present invention, that is, the method for manufacturing carbon nanotubes;

Figure 15 is a cross-sectional view of an improved method of depositing the region shown in Figure 14;

Figure 16 is a cross-sectional view of another modified method of the deposition area shown in Figure 14;

Fig. 17 is a schematic diagram describing a step (growth step) subsequent to the step shown in Fig. 14;

Fig. 18 is a schematic diagram describing the deposition step in the improved method 3 of the present invention, that is, the method for manufacturing carbon nanotubes;

Fig. 19 is a partially enlarged plan view of the surface of the substrate shown in Fig. 18;

Fig. 20 is a schematic diagram describing a step (growing step) subsequent to the step shown in Fig. 18;

Fig. 21 is a schematic diagram describing the step of forming projections in the improved method 4 of the present invention, that is, the method for manufacturing carbon nanotubes;

22A-22C are schematic diagrams describing a step (transferring step) after the step shown in FIG. 21;

Figure 23 is a cross-sectional view illustrating an improved method of the transfer pattern shown in Figures 22A-22C;

Fig. 24 is a cross-sectional view illustrating another modified method of the transfer pattern shown in Figs. 22A-22C;

Fig. 25 is a schematic diagram describing a step (growing step) subsequent to the step shown in Fig. 22C;

Fig. 26 is a schematic diagram describing the protrusion forming step in the improved method 5 of the present invention, that is, the method for manufacturing carbon nanotubes;

Fig. 27 is a schematic diagram describing a step (transfer step) after the step shown in Fig. 26;

Fig. 28 is a schematic diagram describing a step (growth step) subsequent to the step shown in Fig. 27;

Figure 29 is a photomicrograph of the carbon nanotube structure shown in Figure 28;

Figure 30 is a SEM photograph describing the area around the center of the white part shown in Figure 29;

FIG. 31 is a SEM photograph depicting the area surrounding the boundary between the white portion and the black portion shown in FIG. 29;

32A and 32B are schematic diagrams describing the coating formation steps in the modified method 6 of the present invention, that is, the method for manufacturing carbon nanotubes;

33A and 33B are schematic diagrams describing a step (transfer step) subsequent to the step shown in FIG. 32B;

Fig. 34 is a schematic diagram describing a step (growing step) subsequent to the step described in Fig. 33B;

35A-35C are schematic diagrams describing the transfer step in the improved method 7 of the present invention, that is, the method for manufacturing carbon nanotubes;

36A-36C are schematic diagrams describing the catalyst arrangement steps in the improved method 8 of the present invention, that is, the method for manufacturing carbon nanotubes;

Figure 37 is a schematic diagram of a step (growth step) subsequent to the step shown in Figure 36C;

Fig. 38 is a schematic diagram describing the improvement method 9 of the present invention, that is, the protrusion forming step in the method of manufacturing carbon nanotubes;

39A and 39B are schematic diagrams describing a step (planarization step) subsequent to the step shown in FIG. 38;

Fig. 40 is a schematic diagram describing a step (growing step) subsequent to the step shown in Fig. 39;

41 is a cross-sectional view describing an improved method 10 of the present invention, that is, a master in a method for manufacturing carbon nanotubes;

42A and 42B are schematic diagrams describing a step (top surface transfer step) after the step shown in FIG. 41;

Figure 43 is a schematic diagram of a step (growth step) following the step shown in Figure 42B;

Fig. 44 is a schematic diagram describing the step of forming the control layer in the improved method 11 of the present invention, that is, the method for manufacturing carbon nanotubes;

Fig. 45 is a schematic diagram describing a step (growing step) subsequent to the step shown in Fig. 44;

Fig. 46 is a schematic diagram for describing the first example of the present invention, that is, a cathode forming step in a method of manufacturing a field electron emission device and a method of manufacturing an FED;

Fig. 47 is a schematic diagram describing a step (partition groove forming step) subsequent to the step shown in Fig. 46;

Fig. 48 is a schematic diagram describing a step (partition groove forming step) subsequent to the step shown in Fig. 47;

Fig. 49 is a schematic diagram of a brief structure of an FED using a field electron emission device including the cathode shown in Fig. 48;

Fig. 50 is a schematic diagram describing the improved method 12 of the present invention, that is, the step of forming a separation groove;

Fig. 51 is a schematic diagram describing the step of forming a separation groove in the improved method 13 of the present invention, that is, the method for manufacturing a field electron emission device;

Fig. 52 is a schematic diagram describing a step (partition groove forming step) subsequent to the step shown in Fig. 51;

Fig. 53 is a schematic diagram describing a step (cathode forming step) subsequent to the step shown in Fig. 52;

Fig. 54 is a schematic diagram describing the improved method 14 of the present invention, that is, the step of forming a separation groove;

Fig. 55 is a schematic diagram describing the cathode forming step in the improved method 15 of the present invention, that is, the method for manufacturing a field electron emission device and the method for manufacturing an FED;

Fig. 56 is a schematic diagram describing a step (partition groove forming step) subsequent to the step shown in Fig. 55;

Fig. 57 is a schematic diagram describing a brief structure of an FED using a field electron emission device including the cathode shown in Fig. 56;

Fig. 58 is a schematic diagram describing the improved method 16 of the present invention, that is, the step of forming a separation groove;

59A and 59B are schematic diagrams for describing the sixth example of the present invention, i.e., a cathode forming step in a method of manufacturing a field electron emission device and a method of forming an FED;

Fig. 60 is a schematic diagram describing a step (cathode formation step) subsequent to the step shown in Fig. 59B;

FIG. 61 is a schematic diagram describing a step (dividing groove forming step) subsequent to the step shown in FIG. 60;

Fig. 62 is a schematic diagram describing a brief structure of an FED using a field electron emission device including the cathode described in Fig. 61;

63A and 63B are schematic diagrams describing the improvement method 17 of the present invention, that is, the cathode forming steps;

Fig. 64 is a schematic diagram describing the improvement method 18 of the present invention, that is, the step of forming the cathode;

65A and 65B are schematic diagrams describing a step (cathode forming step) subsequent to the step shown in FIG. 64;

66A and 66B are schematic diagrams describing the improvement method 19 of the present invention, that is, the cathode forming steps;

67A and 67B are schematic diagrams describing the reduction/deposition step in the improved method 20 of the present invention, that is, the catalyst arrangement step;

68A and 68B are schematic diagrams describing a seventh example of the present invention, that is, a deposition portion and a separation groove forming step in a method of manufacturing a field electron emission device and a method of manufacturing an FED;

69A-69C are schematic diagrams describing steps subsequent to the step described in FIG. 68B (lead-out electrode forming step);

Fig. 70 is a schematic diagram describing a step (cathode forming step) subsequent to the step described in Fig. 69C;

Fig. 71 is a sectional view illustrating a schematic structure of an FED using a field electron emission device including the cathode shown in Fig. 70;

72A-72C are schematic diagrams describing the improved method 21 of the present invention, that is, the protrusion forming step, the separation groove forming step and the control layer forming step in the catalyst arrangement step;

73A-73C are schematic diagrams describing steps subsequent to the step shown in FIG. 72C (lead-out electrode forming step);

Fig. 74 is a schematic diagram describing a step (cathode forming step) subsequent to the step shown in Fig. 73C;

Fig. 75 is a sectional view describing the structure of a conventional FED.

BEST MODE FOR CARRYING OUT THE INVENTION

Preferred examples of the present invention can be described in detail as follows by referring to the accompanying drawings.

"Methods for making tubular carbon molecules"

[first instance]

First, referring to the accompanying drawings 1-3, the first example of the method for producing tubular carbon molecules of the present invention will be described below. In the method of this example, a carbon nanotube structure including many carbon nanotubes aligned in one direction is formed, and the method of this example includes the "catalyst alignment step" and the "catalyst alignment step" of growing carbon nanotubes using a metal having a catalytic function. growth step", said catalyst aligning step comprising aligning metals having a catalytic function for carbon nanotubes by melting, said melting being achieved by modulating the heat distribution. The resulting carbon nanotube structure can be used, for example, as a cathode of an FED or a recording device.

In this case, the carbon nanotubes include many forms such as a carbon nanotube structure in which many carbon nanotubes are arranged in a fine pattern, a carbon nanotube structure in which an external material is introduced into the carbon nanotubes, or many carbon nanotubes A carbon nanotube structure in which tubes are arranged in a fine pattern and an external material is introduced into the carbon nanotubes. In this example, a carbon nanotube structure in which many carbon nanotubes are arranged in a fine pattern will be described.

Also, in this example, said catalyst arranging step comprises a "melting step" of applying a modulated heat profile 11 to the surface of the substrate 10 to melt the surface of said substrate 10, and a "depositing step", The deposition step is to deposit the second material in place according to the heat distribution 11 , that is, to form a desired pattern through the heat dissipation from the surface of the substrate 10 .

(melting step)

First, the melting step is described with reference to FIG. 1 as follows. In this case, the substrate 10 is made of a first material, and a second material as a deposition material is added to the first material. The second material has a positive segregation coefficient, that is, the melting point of the first material is lowered by adding the second material to the first material, and after heating and melting, the first material solidifies during cooling In this case, the second material retains its properties in the melting zone. In this example, a silicon (Si) substrate can be used as the substrate 10 made of the first material, and as the second material, iron (Fe) can be used as the metal catalyst.

The substrate 10 has a thickness of, for example, 40 nm, and is supported by a support 10A made of, for example, silicon. In the case where the base material 10 has a sufficient thickness, the support body 10A is not necessary.

As the first material, any other semiconductor material (such as germanium (Ge) etc.) and metal material (such as high melting point metal such as tantalum (Ta), tungsten (W) or platinum (Pt) or alloy thereof) can be used instead Silicon above.

As the second material used as a metal catalyst for forming carbon nanotubes, vanadium (V), manganese (Mn), cobalt (Co), nickel (Ni), molybdenum (Mo), tantalum (Ta), tungsten (W ) or platinum (Pt) instead of the aforementioned iron (Fe). Also, yttrium (Y), lutetium (Lu), boron (B), copper (Cu), lithium (Li), silicon (Si), chromium (Cr), zinc (Zn), palladium (Pd), silver ( Ag), ruthenium (Ru), titanium (Ti), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), terbium (Tb), dysprosium (Dy), holmium (Ho) or erbium ( Er). Also, two or more selected from the above materials may be used simultaneously, or a compound of two or more selected from the above materials may be used. Also, metal phthalocyanine compounds, metallocenes or metal salts may be used. Oxide or suicide can be used.

In addition, depending on the application, metal elements or metalloid elements (such as aluminum (Al), silicon (Si), tantalum (Ta), titanium (Ti), zirconium (Zr), niobium (Nb), magnesium (Mg) , boron (B), zinc (Zn), lead (Pb), calcium (Ca), lanthanum (La) or germanium (Ge)) nitrides, oxides, carbides, fluorides, sulfides, nitrogen oxides , carbon-nitride or OC compound as the second material. More specifically, AlN, Al ₂ O ₃ , Si ₃ N ₄ , SiO ₂ , MgO, Y ₂ O ₃ , MgAl ₂ O ₄ , TiO ₂ , BaTiO ₃ , SrTiO ₃ , Ta ₂ O ₅ , SiC, ZnS, PbS, Ge-N, Ge-NO, Si-NO, CaF ₂ , LaF, MgF ₂ , NaF, TiF ₄ , etc. Also, a material including any of these materials as a main component, a mixture of these materials (for example, AlN—SiO ₂ ) may be used. In addition, a magnetic material such as iron (Fe), cobalt (Co), nickel (Ni), or gallium (Gd) may be used.

The heat distribution 11 includes a high temperature region 11H and a low temperature region 11L, which are periodically formed by using radiant energy beams 12 to spatially adjust the surface temperature of the substrate 10 . The energy beam 12 is parallel light with a single wavelength and the same phase. In this example, XeCl excimer laser can be used to obtain high output.

In the present example, said heat distribution 11 is applied by diffracting said energy beam 12 by means of a diffraction grating 13 . The diffraction grating 13 adjusts the energy size spatially by diffracting the energy beam 12, and in the diffraction grating 13, for example, the linear grooves 13A can be distributed on the optical glass plate at a uniform periodic interval P along the one-dimensional direction. In this example, the linear parallel grooves 13A may be distributed on a plate made of quartz material at a period interval P of, for example, 1 micron along the one-dimensional direction, and the diffraction grating 13 is distributed along the one-dimensional direction of the grooves 13A. direction to adjust the energy level of the energy beam 12 . In addition, the diffraction grating 13 is not necessarily limited to a diffraction grating formed with protrusions and depressions (such as grooves), for example, a diffraction grating having a shape through which the energy beam 12 is formed by printing or the like can be used. The transmission part and the non-transmission part that the energy beam 12 cannot pass through.

When such a diffraction grating 13 is used, high temperature regions 11H can be formed linearly along the expanding direction of the grooves 13A, and the high temperature regions are distributed along the one-dimensional direction in which the grooves 13A are distributed. The spatial period T of the heat distribution 11 (ie, the interval (pitch) between the high temperature regions 11H) is determined by the periodic interval P in the diffraction grating 13 and the wavelength λ of the energy beam 12 . The shorter the wavelength λ, or the shorter the period interval P, the more the spatial period T of the heat distribution is reduced.

The energy level of the energy beam 12 is set so that the temperature can reach the temperature at which the surface of the substrate in the low temperature region 11L can melt. Therefore, the entire surface of the substrate 10 can be melted. At this time, when an excimer laser is used as the energy beam 12, the amount of energy may be determined by the radiation amount of the light emitting pulse. In this example, the energy magnitude of the energy beam 12 is, for example, 350 mJ/cm ² , and the number of radiation pulses is ten.

Then, referring to FIG. 2 , the deposition step is described as follows. After the surface of the substrate 10 is melted in the melting step, when the radiation of the energy beam 12 is stopped, the temperature of the surface of the substrate 10 gradually decreases, so that the surface of the substrate 10 can be solidified. At this time, the second material (Fe) moves into the high temperature region 11H, and finally, the second material is deposited in the solidified portion of the high temperature region 11H. Accordingly, the second material is deposited at a position corresponding to the high temperature region 11H, forming a substantially planar-shaped deposition region 14 . Thus, a substrate 15 with a pattern of deposition areas 14 can be obtained.

In this case, "planar shape" means substantially flat, with a height from the surface of said substrate 15 as small as the surface roughness, for example less than 1 nanometer.

When the high temperature regions 11H are linearly arranged in the one-dimensional direction corresponding to the grooves 13A, the deposition regions 14 are formed in a linear pattern corresponding to the one-dimensional direction of the high temperature regions 11H. The width (line width) W of the deposition region 14 (that is, the size of the deposition region 14 in the adjusted direction of the heat distribution region 11) is determined by the content of the second material (iron) in the substrate 10, so the The higher the content of the second material is, the larger the width W of the deposition region 14 is. In principle, the width W of the deposition region 14 can be any value greater than the atomic size of the second material, so by controlling the content of the second material in the substrate 10, the width W of the deposition region 14 can be Smaller than 50 nm, which is not achievable with conventional photolithography.

The specific value of the width W of the deposition region 14 is determined by the second material and the application of the deposition region 14 . For example, as shown in FIG. 3 below, in the case of the carbon nanotube structure 17 in which many carbon nanotubes 16 are linearly arranged by iron deposited in the deposition region 14 as a catalyst, the width of the deposition region 14 W is preferably in the range of 0.4 nm to less than 50 nm, because the minimum size of the carbon nanotube is 0.4 nm.

The width W of the deposition region 14 is more preferably in the range of 0.4 to 30 nanometers, since many carbon nanotubes 16 have a size in the range of 0.4 to 30 nanometers.

Moreover, the width W of the deposition region 14 is more preferably in the range of 0.4-10 nm. This is because the possibility that many carbon nanotubes are densely formed along the width direction of the deposition region 14 decreases, so in the case where the carbon nanotube structure 17 is used as, for example, a field electron emission device (emitter), it is possible to prevent The strength of the electric field on the surface of each carbon nanotube 16 is reduced, and the voltage necessary to be applied for electric field emission can be reduced. Moreover, this is because when the carbon nanotube structure 17 is used as, for example, a recording device (memory), only one carbon nanotube 16 must be formed in one deposition region 14 in the width direction in some cases, so the The size of the carbon nanotubes 16 is preferably matched to the width W of the deposition region 14 .

Moreover, the interval L between the deposition regions 14 (that is, the interval (spacing) between the deposition regions 14 in the adjusted direction of the thermal distribution 11) is determined by the spatial period T of the thermal distribution 11, that is, the diffraction The periodic interval P of the grating 13 and the wavelength λ of the energy beam 12 . The shorter the wavelength λ, or the smaller the period interval P, the more the interval L between the deposition regions 14 will be reduced, and the deposition regions 14 can be formed at fine intervals L, which is a problem for conventional photolithography. legally impossible.

The interval L between the deposition regions 14 is preferably, for example, 100 nm or less. In conventional photolithography, the resolution limit is 50 nanometers, therefore, the smallest pattern formed by conventional photolithography includes, for example, 50 nanometers of protrusions, 50 nanometers of depressions, and 50 nanometers of protrusions, and the The spacing between patterns is twice the resolution limit, ie 100 nm. In addition, the interval L between the deposition regions 14 is more preferably 50 nm or less. This is because the resolution limit of conventional electron beam lithography is about 25 nanometers, so the interval between the smallest patterns formed by conventional electron beam lithography is twice the resolution limit, ie, 50 nanometers.

This completes the catalyst alignment step and forms a substrate 15 including the deposition area 14 on the substrate 10 .

(grow step)

Then, referring to Fig. 3, the growth step is described as follows. Carbon nanotubes 16 are grown on said substrate 15 by a CVD (Chemical Vapor Deposition) method. As a growth environment, for example, methane (CH ₄ ) can be used as a carbon-containing compound, which is a material of carbon nanotubes 16, iron deposited on the deposition area 14 is used as a catalyst, and the growth step is performed at 900° C. for 15 minutes . The carbon nanotubes 16 grow only in the deposition area 14 , so a carbon nanotube structure 17 in which many carbon nanotubes 16 are linearly arranged according to the pattern of the deposition area 14 is formed on the substrate 15 . The diameter of the carbon nanotubes 16 is determined by the carbon-containing compound used as the material of the carbon nanotubes 16 and the growth environment.

Thus, in this example, a pattern of deposition areas 14 made of iron having a catalytic function for the formation of said carbon nanotubes 16 is formed and aligned by melting by modulating the heat distribution Reached, the carbon nanotubes 16 are grown through the pattern of the deposition region 14, so by controlling the heat distribution 11, the pattern of the deposition region 14 with a fine width W can be formed at a fine interval L, and the fine width W and fine The interval L is difficult to achieve by conventional photolithography, and a carbon nanotube structure 17 in which carbon nanotubes 16 are regularly arranged corresponding to the pattern of the deposition region 14 can be formed on the substrate 15 .

Moreover, the substrate 15 including the pattern of the deposition area 14 can be obtained by a dry method, so this example can have some advantages, such as easier production, better reproducibility, and reduced cost, compared to a process using conventional photolithography. .

Furthermore, in this example, after applying the heat profile 11 to the surface of the substrate 10 made of silicon containing iron as an additive to melt the surface of the substrate 10, the surface of the substrate 10 The heat is dissipated, so iron can be selectively deposited on the positions corresponding to the hot zones 11 to form a pattern of deposition regions 14 having a substantially planar shape.

In addition, in this example, the heat distribution 11 is applied by diffracting the energy beam 12, so when the period interval P in the diffraction grating 13 is reduced, the spatial period T of the heat distribution 11 It is easy to control, and the interval L between the deposition regions 14 is finer, so the accuracy is higher.

[Second instance]

Then, a second example of the present invention is described as follows. The example further includes a height homogenization step after forming the carbon nanotube structure 17 according to the first example, and forming the tip into an open tip (open end), the height homogenization step is at a predetermined A flat surface forms the tips of the carbon nanotubes 16 .

In this example, “height” means the position of the tip of the carbon nanotube 16 , that is, the distance between the surface of the substrate 10 and the tip of the carbon nanotube 16 . Therefore, the height of the carbon nanotubes 16 may be different from the length of the carbon nanotubes 16 (ie, the actual size in the extending direction).

(high homogenization step)

The height homogenization step is described as follows with reference to FIGS. 4A and 4B . First, as shown in FIG. 4A , a fixed layer 18 is formed around the carbon nanotubes 16 to fix the carbon nanotubes 16 through the fixed layer 18 . As the material of the fixed layer 18, for example, an insulating material (such as silicon dioxide (SiO ₂ ), silicon nitride (SiN), polyimide, polymethyl methacrylate (PMMA) or a metal oxide film can be used. ) or semiconductor materials such as silicon or germanium. As a method of forming the fixed layer 18 , for example, a plasma-enhanced CVD (PECVD) method, a PVD (Physical Vapor Deposition) method, a SOG (spin on glass) method, or the like can be used. The thickness of the fixing layer 18 is not particularly limited.

Next, as shown in FIG. 4B , for example, the carbon nanotubes 16 are polished together with the fixed layer 18 by a CMP (Chemical Mechanical Polishing) method. Therefore, the tips of the carbon nanotubes 16 are arranged in the same plane PL, and the tips are opened by polishing to form an open tip 16A.

Accordingly, there can be obtained carbon nanotubes 16 arranged in a desired pattern on the substrate 15, the tips of which are formed in a predetermined plane PL, and the tips are formed as open tips 16A. Therefore, the heights of the carbon nanotubes 16 in the carbon nanotube structure 17 can be uniformed. Also, the fixing layer 18 is formed around the carbon nanotubes 16 to fix the carbon nanotubes through the fixing layer 18 . Therefore, the carbon nanotubes 16 can be tougher, and the carbon nanotube structures 17 can be handled more easily.

In this example, the tips of the carbon nanotubes 16 are arranged in the same plane PL. For example, in the case where the carbon nanotube structure 17 is used as an FED, even if there are carbon nanotubes 16 grown at an angle to the surface of the substrate 10, electric field emission of all the carbon nanotubes 16 can be performed, thereby obtaining Uniform emission characteristics. Also, when the tip of the carbon nanotube 16 is an open tip 16A, the electric field emission characteristic can be better, so that electric field emission can be performed at a low voltage.

In this example, a case is described in which the fixed layer 18 is used as a planar layer when polishing is performed as shown in FIG. 4B; however, the fixed layer 18 that is not polished and in the state shown in FIG. 4A can be used for, for example, an FED. In this case, the carbon nanotubes 16 are fixed by the fixing layer 18, so the carbon nanotubes 16 can be more rigid, and the carbon nanotube structure 17 can be handled easily.

[Third example]

Next, a method for producing carbon nanotubes of a third example of the present invention is described as follows. In the method of the present invention, desired materials are included in the tip portions of the carbon nanotubes 16 in the growth step of the first example. The resulting carbon nanotube structure 17 can be used for many purposes depending on, for example, the material introduced, in this example, by introducing a magnetic material such as iron, so that the carbon nanotube structure 17 can be used as a recording device.

As a method of introducing a desired material when growing the carbon nanotubes 16, a VLS (Vapor-Liquid-Solid) method which is one of CVD methods can be used. The VLS method uses a mechanism of decomposing a gas containing carbon to form an alloy drop including carbon and a metal having a catalytic function, on which the carbon nanotube 16 grows in one direction. In the VLS method, iron as a catalyst moves to the tips of the carbon nanotubes 16 when the carbon nanotubes 16 grow, so iron can be introduced into the tips of the carbon nanotubes 16 . Thus, the carbon nanotube structure 17 (the carbon nanotubes 16 including iron in their tips arranged in a desired pattern) can be obtained. The phenomenon that iron is introduced into the tips of the carbon nanotubes 16 is described above, Masafumi Ata and three others, Japanese Journal of Applied Physics (Jpn.J.Appl.Phys.), 1995, Vol. 34, pp. 4207-4212).

In this example, iron, for example, is deposited in the deposition region 14 , and iron is introduced into the tips of the carbon nanotubes 16 when the carbon nanotubes 16 are grown by using iron as a catalyst. Thus, when the material deposited in the deposition region 14 is varied, desired material can be introduced into the tips of the carbon nanotubes 16 . As the desired material introduced into the carbon nanotubes 16, any material that can be used as a metal catalyst for forming carbon nanotubes can be used, and specific examples of the desired materials are the same as the examples of the second material described in the first example. .

Also, depending on the application, the dielectric material described in the first example as an example of the second material may be used as the material introduced into the carbon nanotubes 16 .

Therefore, in this example, when the carbon nanotube 16 grows, iron is introduced into the tip of the carbon nanotube 16, so the carbon nanotube structure 17 (the carbon nanotube in which iron is introduced into the tip) can be obtained. 16 arranged in the desired pattern).

"Method of Manufacturing Recording Device"

[Fourth example]

Then, a method of manufacturing a recording device of a fourth example of the present invention is described as follows. The method of the present example includes an inserting step of inserting a magnetic material into the tip portion of the carbon nanotube 16 from the open tip 16A of the carbon nanotube 16, the carbon nanotube 16 having a uniform height obtained from the first Two instances. The obtained carbon nanotube structure 17 can be used, for example, in a recording device.

(insert step)

Referring to Figures 5A and 5B, the insertion step is described as follows. First, as shown in FIG. 5A, a thin film 19 made of, for example, a magnetic material such as iron is formed on the fixed layer 18 by, for example, spin coating, vapor deposition, or PVD to block the tip of the opening. 16A. At the same time, the film 19 enters the carbon nanotube 16 from the opening tip 16A.

Then, as shown in FIG. 5B , the thin film 19 is polished by, for example, a CMP method until the fixed layer 18 is exposed, thereby removing the thin film 19 except for the part that enters the carbon nanotubes 16 . Accordingly, the magnetic layer 19A made of iron is inserted around the tip of the carbon nanotube 16, and the carbon nanotube 16 can be obtained in which a desired material is inserted at least in the tip portion thereof.

This forms the recording device 20 of this example. The recording device 20 includes carbon nanotubes 16 arranged in a desired pattern on the substrate and a magnetic layer 19A composed of a magnetic material inserted into at least tip portions of the carbon nanotubes 16 . The recording device 20 includes the carbon nanotube structure 17, wherein the carbon nanotubes 16 are arranged in a desired fine pattern, and a magnetic layer 19A made of iron is inserted into each carbon nanotube 16, so the length of the magnetization is It can have a small size, which cannot be achieved by conventional photolithography, so the recording density is very high. The magnetic layer 19A inserted into each carbon nanotube 16 is separated from the magnetic layer 19A in other adjacent carbon nanotubes 16, so that information can be accurately read and written on each magnetic layer 19A.

Also, in the case of the second example, the tips of the carbon nanotubes 16 are formed in a predetermined plane, the tips being the open tips 16A. Therefore, the heights of the carbon nanotubes 16 in the carbon nanotube structure 17 can be uniform. In addition, the fixing layer is formed around the carbon nanotubes 16 to fix the carbon nanotubes 16 through the fixing layer 18 . Therefore, the carbon nanotubes 16 can be more rigid, and the recording device 20 can be handled easily.

FIG. 6 depicts an example of a recording state in the recording device 20. As shown in FIG. In the recording device 20, recording (writing) and reproduction (reading) of signals can be performed by controlling the magnetization direction of the magnetic layer 19A as indicated by arrows. When writing and reading signals, said signals can be written, for example, by generating a magnetic flux in a predetermined direction with a fine coil, said signals can be read by a GMR head, or write and read signals can be passed through so-called magnetic coils. light system to complete.

Writing and reading on said recording device 20 by eg a magneto-optical system can be as follows. Writing on the recording device 20 is accomplished through the following steps. The temperature of the magnetic layer 19A made of iron is raised to the Curie temperature to align the magnetization direction of the magnetic layer 19A in a predetermined direction by a bias magnetic field (erasing mode). Afterwards, the magnetization direction of the bias field is aligned in the direction opposite to the erasure mode, and the temperature of only the magnetic layer 19A of the specific carbon nanotube 16 is increased by using a laser beam whose spot diameter passes through an optical lens ( not shown), and the irradiation with the laser beam is stopped, thereby changing the magnetization direction of the magnetic layer 19A to the direction opposite to that at the time of deletion. Also, the read operation from the recording device 20 is performed by, for example, the following steps. The magnetic layers 19A in the carbon nanotubes 16 are irradiated with a laser beam to monitor the Kerr rotation angle of the emitted light of the laser beam, so that the magnetization direction of each magnetic layer 19A can be obtained as a reproduced signal. Meanwhile, in this example, the magnetic layer 19A is separated by the carbon nanotubes 16 , so the predetermined magnetization direction can be kept stable without affecting the magnetic layer 19A in the adjacent carbon nanotubes 16 .

Therefore, in this example, the carbon nanotube structure 17 (in which the carbon nanotubes 16 are arranged in a desired fine pattern) is included, and the magnetic layer 19A made of iron is inserted into each carbon nanotube 16, so A recording device 20 with an extremely high recording density can be obtained. Moreover, the magnetic layer 19A is separated by the carbon nanotubes 16 , so it can maintain a stable predetermined magnetization direction for a long time without affecting the magnetic layer 19A in the adjacent carbon nanotubes 16 . Therefore, the reliability of the recording device is improved.

"Improved method for making tubular carbon molecules"

Before describing the methods of manufacturing field electron emission devices and manufacturing FED, the improved method of manufacturing carbon nanotubes (1-11) of the first example of the present invention is described as follows. Carbon nanotubes produced by these improved methods can be used to produce carbon nanotubes 16 whose heights are homogenized as shown in FIGS. 4A and 4B of the second example. Also, by using the carbon nanotubes manufactured by the improved method, it is possible to manufacture the carbon nanotubes 16 in which the desired material is inserted into the tip portion thereof as described in the third example, or to manufacture the fourth example shown in FIG. 5A- 6 recording device 20 . In addition, the carbon nanotubes produced by the improved method can be applied to field electron emission devices and FEDs described below.

[Improvement method 1]

First, improvement method 1 is described as follows with reference to FIGS. 7-13 . In the improved method, the energy magnitude of the energy beam in the melting step is modulated in two-dimensional directions, that is, the X direction and the Y direction, so as to apply the X-direction heat distribution 31X and the Y-direction heat distribution 31Y to the base material 10 On the surface.

(melting step)

First, the melting step is described with reference to FIG. 7 as follows. The X direction 31X includes an X direction high temperature region 31HX and an X direction low temperature region 31XL, which are periodically formed by adjusting the surface temperature of the substrate 10 in the X direction. The Y-direction heat distribution 31Y includes a Y-direction high-temperature region 31HY and a Y-direction low-temperature region 31YL, which are periodically formed by adjusting the surface temperature of the substrate 10 in the Y-direction.

The X-direction thermal distribution 31X and the Y-direction thermal distribution 31Y are applied, for example, by diffracting the energy beam 12 through a diffraction grating 32 in which non-transmissive portions 32A and transmissive portions 32B are arranged in two-dimensional directions . As the diffraction grating 32 , a diffraction grating in which, for example, a mask through which the energy beam 12 cannot pass is printed on the non-transmission portion 32A or the like can be used.

FIG. 8 depicts a state in which a heat distribution 33 is formed by stacking an X-direction temperature distribution 31X and a Y-direction temperature distribution 31Y on the surface of the substrate 10 . As shown in FIG. 8, a heat distribution 33 including a high-temperature region 33H and a low-temperature region 33L is formed on the surface of the substrate 10. The positions of the high-temperature region 33H are the X-direction high-temperature region 31XH and the Y-direction high-temperature region 31YH. The position where the low-temperature region 33L is stacked on each other is the position where the X-direction low-temperature region 31XL and the Y-direction low-temperature region 31YL are stacked on each other. Therefore, the high temperature regions 33H are arranged two-dimensionally along the direction in which the non-transmitting parts 32A and the transmitting parts 32B are arranged.

The spatial period TX in the X direction of the heat distribution 33 (that is, the interval (pitch) between the high temperature regions 33H in the X direction) is determined by the periodic interval PX in the X direction of the grating 32 and the wavelength λ of the energy beam 12 . Moreover, the spatial period TY in the Y direction of the heat distribution 33 (that is, the interval (pitch) between the high temperature regions 33H in the Y direction) is determined by the spatial interval PY in the Y direction in the diffraction grating 32 and the wavelength λ of the energy beam 12 Decide. The smaller the wavelength λ, or the smaller the periodic intervals PX and PY, the more the spatial intervals TX and TY in the thermal profile 33 are reduced. In this example, the periodic interval PX in the X direction of the diffraction grating 32 represents the sum of the size of a non-transmissive portion 32A in the X direction and the size of a transmission portion 32B in the X direction, and the Y direction in the diffraction grating 32 is The periodic interval PY above represents the sum of the size of one non-transmissive portion 32A in the Y direction and the size of one transmissive portion 32B in the Y direction.

In the diffraction grating 32, the period interval PX in the X direction and the period interval PY in the Y direction can be set separately. Therefore, as shown in FIG. 9 , the space interval TX in the X direction and the space interval TY in the Y direction in the heat distribution 33 may be set separately.

As the diffraction grating 32 , instead of the diffraction grating in which the non-transmitting portion 32A and the transmitting portion 32B are formed by mask printing, a diffraction grating formed with a concave portion or a convex portion may be used. In the case of using a diffraction grating 32 forming convex and concave portions, the periodic interval in the X direction in the diffraction grating 32 represents the interval (pitch) between the concave portions (or convex portions) in the X direction, The periodic interval PY in the Y direction in the diffraction grating 31 represents the interval (pitch) between concave portions (or convex portions) in the Y direction.

The energy level of the energy beam 12 is set so that the temperature reaches a temperature at which the surface of the substrate 10 in the low temperature region 33L can melt. Therefore, the entire surface of the base material 10 can be melted. At this time, when an excimer laser is used as the energy beam 12, the magnitude of the energy can be controlled by the amount of light-emitting pulse irradiation.

(deposition step)

Then, the deposition step is described as follows with reference to FIGS. 10 and 11 . In the melting step, when the irradiation with the energy beam is stopped after the surface of the substrate 10 is completely melted, the heat of the surface of the substrate 10 is dissipated, so that the second material is deposited on the surface corresponding to In the position of the heat distribution 33 , that is, a region corresponding to the high temperature region 33H, a deposition region 34 having a substantially planar shape is thus formed. Thus, a substrate 35 with a pattern of deposition areas 34 is obtained.

When the high-temperature regions 33H are arranged two-dimensionally on the surface of the substrate 10, the deposition regions 34 are formed in a dot pattern corresponding to the two-dimensionally arranged high-temperature regions 33H. on the surface of the substrate 10. In the deposition region 34 , the dimension (diameter) DX in the X direction and the dimension (diameter) DY in the Y direction are determined by the content of the second material in the substrate 10 . The greater the content of the second material, the greater the increase in the dimensions DX and DY of the deposition region 34 . The dimensions DX and DY of the deposition region 34 can be any value greater than the atomic size of the second material, so, by controlling the content of the second material in the substrate 10, the DX and DY of the deposition region 34 The DY size can be smaller than 50nm, which is impossible to achieve by conventional photolithography.

The specific values of the dimensions DX and DY of the deposition area are determined by the second material and the use of the deposition area 34; but, for example, as shown in FIG. When the carbon nanotube structure 37 (in which many carbon nanotubes 36 are arranged two-dimensionally) is formed from iron, the dimensions DX and DY of the deposition region 37 are preferably in the range of 0.4 nanometers to less than 50 nanometers. This is because the diameter of the carbon nanotubes 36 is at least 0.4 nm.

The dimensions DX and DY of the deposition region 34 are more preferably 0.4-30 nm. This is because many carbon nanotubes 36 have a diameter of 0.4-30 nm.

Also, the dimensions DX and DY of the deposition region 34 are more preferably in the range of 0.4-10 nm. This is because the possibility of dense formation of many carbon nanotubes 16 in the deposition region 34 along the X direction or the Y direction is reduced, so when the carbon nanotube structure 37 is used as, for example, a field-induced electronic device, each The electric field strength on the surface of the carbon nanotubes 36 decreases and reduces the voltage that must be applied for said electric field emission. Moreover, this is because when the carbon nanotube structure 37 is used as, for example, a recording device (memory), only one carbon nanotube 36 must be formed in one deposition region 34 in the X direction and the Y direction in some cases, Therefore, the diameter of the carbon nanotubes 36 is preferably matched with the dimensions DX and DY of the deposition region 34 .

Moreover, in the deposition area 34, the interval LX in the X direction and the interval LY in the Y direction are determined by the spatial periods TX and TY in the thermal distribution 33, that is, the spatial intervals PX and TY in the diffraction grating 32 PY and the wavelength λ of the energy beam. The shorter the wavelength λ, or the smaller the spatial intervals PX and PY in the diffraction grating 32, the more the intervals LX and LY between the deposition regions 34 are reduced, and the deposition regions 34 can be formed Fine spacing LX and LY, which cannot be obtained by conventional photolithography.

The intervals LX and LY between the deposition regions 34 are preferably, for example, 100 nm or less. As mentioned above, in conventional photolithography, the resolution limit is 50 nanometers, therefore, the smallest pattern formed by conventional photolithography includes, for example, 50 nanometers of protrusions, 50 nanometers of depressions and 50 nanometers of protrusions, The spacing between the patterns is twice the resolution limit, ie 100 nanometers. Also, the intervals LX and LY between the deposition regions 34 are more preferably 50 nm or less. This is because the resolution limit in conventional electron beam lithography is about 25 nanometers, so the interval between the smallest patterns formed by conventional electron beam lithography is twice the resolution limit, ie, 50 nanometers.

This completes the catalyst alignment step and forms a substrate 35 including the deposition area 34 on the substrate 10 .

As shown in FIG. 9 , when the spatial period TX in the X direction and the spatial period TY in the Y direction in the heat distribution 33 are separately set, the deposition area 34 can be set according to the spatial period TX and the spatial period TY as shown in FIG. 13 . TY is formed as an ellipse.

(grow step)

Then, referring to Fig. 12, the growth step is described as follows. Many carbon nanotubes 36 are grown on the substrate 35 by CVD. The growth conditions may eg be the same as in the first example described. The carbon nanotubes 36 are only grown in the deposition area 34, so the carbon nanotube structure 17 is formed on the substrate 35 (wherein the carbon nanotubes 36 are formed according to the pattern of the deposition area 34 dimensional arrangement).

Therefore, in the improved method, the energy size of the energy beam 12 is adjusted along the two-dimensional direction to form the heat distribution 33, so the pattern of the deposition regions 34 arranged along the two-dimensional direction is formed on the surface of the substrate 10 superior.

Moreover, the energy beam 12 is diffracted by the diffraction grating 32 to form a thermal distribution 33, so when the periodic spaces PX and PY in the diffraction grating 32 decrease, the spatial periods TX and TY in the thermal distribution 33 Can be easily controlled, and the intervals LX and LY between the deposition regions 34 can be reduced.

[Improvement method 2]

Then, referring to FIGS. 14-17 , the improvement method 2 is described as follows. In the improved method, heat is dissipated from the surface of the base material 10 to form protrusions on the surface of the base material 10, and the second material is deposited on tip portions of the protrusions.

(melting step)

First, a melting step is performed, for example, as shown in Fig. 1 in the first example. At this time, the energy level of the energy beam 12 is controlled so as to exceed a certain value. For example, when an excimer laser is used as the energy beam as shown in the first example, the amount of energy can be controlled by controlling the number of light-emitting pulse irradiations, and in this improved method, the number of pulse irradiations is 100 .

(deposition step)

When the surface of the base material 10 is melted in the melting step, when the irradiation with the energy beam 12 is stopped, as shown in FIG. 14 if the energy level of the energy beam 12 applied in the melting step exceeds a certain amount , as shown in FIG. 14 , the surface of the substrate 10 corresponding to the high temperature region 11H protrudes to form a protrusion 41 .

When the high-temperature regions 11H are linearly arranged in one-dimensional direction corresponding to the grooves 13A, the protrusions 41 are formed in a pattern of linear ribs (protruding sides) corresponding to the grooves 13A. The high temperature regions 11H are arranged in one-dimensional direction. Protrusions 41 near the surface of the substrate 10 solidify so that the second material (iron) is deposited around the tip and part of the tip solidifies to form the deposition area 42 . Therefore, the deposition area 42 is formed at the tip portion of the protrusion 41 . Here, the tip portion is a portion including the tip of the protrusion in which the protrusion 41 is cut along a horizontal plane H (refer to FIGS. 15 and 16 ) parallel to the surface of the substrate 10 . For example, the deposition area 42 may be formed only in the tip of the protrusion 41 as shown in FIG. 14 , or the entire protrusion 41 may be the deposition area 42 as shown in FIG. 15 . Alternatively, as shown in FIG. 16, the deposition area 42 may be formed in a portion of the protrusion 41 from the tip to the middle point.

This resulted in a substrate 43 comprising a pattern of protrusions 41 in which deposited regions 42 made of iron were formed at least at tip portions of said protrusions 41 .

Here, "protrusion" means a protrusion from the surface of the substrate 43 with a height of 1 nm or more, which is higher than that of the planar shape deposition region 14 in the first example.

As described in the first example, the width (line width) W of the deposition region 42 (that is, the size of the deposition region 42 along the modulation direction of the heat distribution 11) is determined by the second material (iron ) content, the greater the content of the second material (iron), the more the width W of the deposition region 42 increases. In principle, the width of the deposition region 42 can be any value greater than the atomic size of the second material, so by controlling the content of the second material in the substrate 10, the width W of the deposition region 42 can be Less than 50 nanometers, which cannot be achieved by conventional photolithography.

In the improved method, unlike the first example, the deposition region 42 is a protrusion 41, and the cross-sectional area of the deposition region 42 decreases toward its tip, so the width of the deposition region 42 can be easily reduced. .

Like the width W of the deposition region 14 described in the first example, the specific value of the width W of the deposition region 42 is determined by the second material and the application of the deposition region 42 . For example, as shown in FIG. 17, when forming a carbon nanotube structure 45 in which many carbon nanotubes 44 are linearly arranged by using iron deposited in the deposition region 42 as a catalyst, the width W of the deposition region 42 is preferably at In the range of 0.4 nm to less than 50 nm, more preferably 0.4-30 nm, still more preferably 0.4-10 nm, for the same reasons as described in the first example.

Moreover, the interval L between the protrusions 41 (i.e. the interval (pitch) between the deposition areas 42 in the modulation direction of the heat distribution 11) is determined by the periodic interval T of the heat distribution 11 (i.e. the diffraction The spacing P in the grating 13 is determined by the wavelength λ) of the energy beam 12 . The shorter the wavelength λ, or the smaller the periodic interval P, the more the interval L between the protrusions 41 is reduced, and the protrusions 41 and the deposition regions 42 can form a fine interval, which is It cannot be achieved by conventional photolithography. For example, the interval L between the protrusions 41 is preferably 100 nm or less, more preferably 50 nm or less, for the same reason as described in the first example.

The catalyst arranging step is thus completed to form the substrate including the deposition region 42 on the tip portion of the protrusion 41 formed on the substrate 10 .

(grow step)

Referring to FIG. 17, many carbon nanotubes 44 are grown on the substrate 43 by CVD. The growth environment was the same as the first example described. The carbon nanotubes 44 are only grown in the deposition area 42, so the carbon nanotube structure 45 is formed, wherein many carbon nanotubes 44 are linearly arranged on the tipmost part of the protrusion 41 of the substrate 43 ( extreme tip portion).

Therefore, in the improved method, the protrusion 41 (wherein at least the tip portion thereof is made of the second material (iron)) is formed in a predetermined position of the base material 10, so that, unlike the pattern The width of the deposition region 42 is finer than in the case of being formed in a planar shape, and a finer pattern can be formed than in the first example and the modified method 1.

[Improvement method 3]

Next, referring to FIGS. 18-20 , the improved method 3 is described as follows. In the modified method, protrusions arranged in a two-dimensional direction are formed on the surface of the substrate 10, and the second material is deposited on tip portions of the protrusions.

(melting step)

First, for example, a melting step is performed as in Modified Method 1 shown in FIGS. 7 and 8 . At this time, control the energy beam 12 and the magnitude of the energy as in the improved method 2 so as to exceed a certain amount.

(deposition step)

In the melting step, when the irradiation with the energy beam 12 is stopped after the surface of the base material 10 is melted, if the energy magnitude of the energy beam 12 applied in the melting step exceeds a specific amount, as shown in FIGS. 18 and 19 As shown, the surface of the substrate 10 protrudes correspondingly to the high temperature region 33H, forming a protrusion 51 .

When the high-temperature regions 33H are arranged on the surface of the substrate 10 along the two-dimensional direction, the protrusions 51 are formed in a conical pattern, and are arranged on the surface of the substrate 10 corresponding to the high-temperature regions 11H along the two-dimensional direction. superior. The portion of the protrusion 51 near the surface of the substrate 10 solidifies so that the second material is deposited around the tip and the tip of the tip solidifies forming a deposition area 52 . Accordingly, the deposition area 52 is formed in the tip portion of the protrusion 51 . Important and specific examples of the tip portion are the same as those described with reference to FIGS. 15 and 16 in Modification Method 2. FIG.

This resulted in a substrate 53 comprising a pattern of protrusions 51 in which deposited areas 52 made of iron were formed at least in the tip portion.

In the deposition area 52, the dimension (diameter) DX in the X direction and the dimension (diameter) DY in the Y direction are determined by the content of the second material (iron) in the substrate 10, the second material The greater the (iron) content, the more the dimensions DX and DY of the deposition area 52 are increased. In principle, the dimensions DX and DY of the deposition region 52 can be any value greater than the atomic size of the second material, so by controlling the content of the second material in the substrate 10, the size of the deposition region 52 DX and DY can be smaller than 50 nanometers, which cannot be achieved by conventional photolithography.

Like the dimensions DX and DY of the deposition region 34 described in the improved method 2, the specific values of the dimensions DX and DY of the deposition region 52 are determined by the second material and the application of the deposition region 52 . For example, as shown in FIG. 20, when the carbon nanotube structure 55 (in which many carbon nanotubes 54 are arranged in a two-dimensional direction) is formed by using iron deposited in the deposition region 52 as a catalyst, the deposited The dimensions DX and DY of the region 52 are preferably in the range of 0.4 nm to less than 50 nm, more preferably 0.4-30 nm, still more preferably 0.4-10 nm, for the same reason as described in Modified Method 2.

Moreover, the interval LX in the X direction and the interval LY in the Y direction between the protrusions 51 (that is, the deposition area 52 ) are determined by the spatial periods TX and TY of the thermal distribution 33 , that is, the diffraction grating The periodic intervals PX and PY in 32 and the wavelength λ of said energy beam 12 . The shorter the wavelength λ, or the smaller the periodic intervals PX and PY in the diffraction grating 32, the more the intervals LX and LY between the protrusions 51 (that is, the deposition regions 52) are reduced. 51 and deposition area 52, fine spacing LX and LY can be formed, which cannot be obtained by conventional photolithography. The intervals LX and LY between the protrusions 51 (ie, the deposition regions 52 ) are preferably 100 nm or less, more preferably 50 nm or less, for the same reason as described in the improved method 2.

This completes the catalyst arranging step, forming a substrate 53 comprising a deposition area 52 located at the tip portion of the protrusion 5 .

(grow step)

Next, referring to FIG. 20, many carbon nanotubes 54 are grown on the substrate 53 by CVD. The growth environment was the same as that described in the first example. The carbon nanotubes 54 are only grown in the deposition area 53, thus forming the carbon nanotube structure 55, wherein the carbon nanotubes 54 are arranged two-dimensionally on the protrusions 51 of the substrate 53 the most advanced part.

Therefore, in the improved method, the pattern of the protrusions 51 (wherein at least the tip portion thereof is made of the second material) is arranged in a predetermined position of the base material 10 in the two-dimensional direction, so, relatively The deposition region 52 having a finer size is formed than the planar shape deposition region in the first example and the modified method 1 described above.

[Improvement method 4]

Then, referring to Figs. 21-25, the improvement method 4 is described as follows. In this modified method, a raised pattern made of a transfer material is formed on the surface of a base material 10 made of a transfer material (in this case, a catalyst), and the raised pattern is used for transfer. The master plate is used to transfer the pattern of the master plate for transfer onto the base material to be transferred, so as to obtain the base material, and grow carbon nanotubes on the base material.

More specifically, in this example, the catalyst alignment step includes a "melting step", a "protrusion forming step" and a "transferring step", said "melting step" including said heat distribution to be modulated according to a desired pattern 11 is applied to the surface of the substrate 10 to melt the surface of the substrate 10, the "protrusion forming step" includes forming a protrusion at a position corresponding to the heat distribution 11, the "transfer printing The step" includes transferring the pattern of the master plate for transfer onto the substrate to be transferred to form the substrate.

(melting step)

First, the melting step was performed as described in Modified Method 2. At this time, the substrate 10 is made of iron used as a catalyst in this example.

The material of the substrate 10 may be, for example, any material having functions including being used as a metal catalyst for forming carbon nanotubes, specific examples of which are the same as those described in the first example as the second material The example is the same.

(Protrusion forming step, Mother plate forming step)

Then, referring to FIG. 21, the protrusion forming step is described as follows. In the melting step, after the surface of the substrate 10 is melted and the irradiation with the energy beam 12 is stopped, the surface temperature of the substrate 10 gradually decreases, so that the surface of the substrate 10 is solidified , at this time, when the energy magnitude of the energy beam 12 applied in the melting step exceeds a certain value, the protrusion 64 protruding from the surface of the base material 10 is formed in a position corresponding to the high temperature region 11H, A transfer master 65 having protrusions 64 is formed on the surface of the substrate 10 .

When the protrusions 64 are linearly arranged in the one-dimensional direction corresponding to the grooves 13A, the protrusions 64 are formed in a linear rib (raised side) pattern arranged in the one-dimensional direction. The width (line width) W of the protrusion 64 (ie, the bottom end portion size of the protrusion in the modulation direction of the heat distribution 11 ) is determined by the melting temperature and the cooling rate. The melting temperature can be controlled by the energy of the energy beam 12 (that is, in the case of using an excimer laser, the number of pulses irradiated), the higher the melting temperature, the more the width W of the protrusion 64 increases . The cooling rate is controlled by a method of placing the base material 10 or a fixture equipped with the base material 10 in a vacuum, a method of gas flow, or a method of cooling in water or liquid nitrogen. 1. A method of heating while cooling slowly, the faster the cooling rate is, the more the width W of the protrusion 64 increases. In principle, the width W of the protrusion 64 can be any value larger than the atomic size of the material of the substrate 10, so by controlling the melting temperature and cooling rate, the width W of the protrusion 64 can be smaller than 50 nanometers, which cannot be achieved by conventional photolithography.

The specific value of the width W of the protrusion 64 is determined by the application of the substrate described below. For example, when forming a carbon nanotube structure, the width W of the protrusion 64 is preferably in the range of 0.4 nanometers to less than 50 nanometers, more preferably 0.4-30 nanometers, and still more preferably 0.4-10 nanometers. Same reason as described in the first example.

Moreover, the interval L between the protrusions 64 (that is, the interval (pitch) between the protrusions 64 in the modulation direction of the heat distribution 11) is determined by the spatial period T of the heat distribution 11 (that is, the diffraction The periodic interval P of the grating 13 is determined by the wavelength λ) of the energy beam 12 . The shorter the wavelength λ, or the shorter the period interval P, the more the interval L between the protrusions 64 is reduced, so the protrusions 64 can form a fine interval L, which is a conventional photolithography method. unattainable. For example, the interval L between the protrusions 64 is preferably 100 nm or less, more preferably 50 nm or less, for the same reason as in the first example.

(transfer step)

Then, referring to FIGS. 22A-22C , the transfer step is described as follows. First, for example, as shown in FIG. 22A , a base material 71 to be transferred on which a wiring pattern of a conductive film 72 is formed in advance is prepared.

Then, as shown in FIG. 22B, the bumps 64 of the master 65 and the conductive film 72 of the substrate 71 to be transferred are closely opposed to each other. At this time, in order to improve transfer properties, it is preferable to apply force in the direction of arrow A, if necessary. Also, heat treatment is preferably performed because the transfer property can be further improved.

Afterwards, when the master plate 65 is pulled away from the substrate 71 to be transferred, as shown in FIG. 22C , the tip portions of the protrusions 64 are transferred onto the substrate 71 to be transferred. Thus, a substrate 74 is formed in which the transfer pattern 73 made of catalyst metal (iron) is formed on the substrate 71 to be transferred. Therefore, many substrates 74 can be produced by transferring the pattern of the protrusions 64 onto many substrates 71 to be transferred through one master 65 . When the protrusion 64 is worn out by repeated transfer, the melting step and the protrusion forming step are repeated again to restore the shape of the protrusion 64 .

Herein, "the tip portion of the protrusion 64" means the portion including the tip of the protrusion 64, wherein the protrusion 64 is cut along a horizontal plane H parallel to the surface of the substrate 10 (refer to FIG. 23 and 24). Thus, for example, as shown in Figure 22C, only the tips of the protrusions can be transferred to the substrate 71 to be transferred, or as shown in Figure 23, the entire protrusion 64 can be transferred to the substrate to be transferred. Printed substrate 71. Alternatively, as shown in FIG. 24, the portion from the tip to the middle point of the protrusion 64 may be transferred onto the substrate 71 to be transferred.

This completes the catalyst alignment step.

(grow step)

The transfer pattern 73 is formed on the substrate 71 to be transferred. After the substrate 74 is formed, for example, as shown in FIG. On the substrate 74, a carbon nanotube structure 76 is formed, wherein many carbon nanotubes 75 are arranged linearly. Therefore, the carbon nanotube structure 76 formed on the conductive film 72 can be used as a field electron emission device.

Therefore, in this modified method, said heat distribution 11 is applied on the surface of a substrate 10 made of catalyst metal so that after melting the surface of said substrate 10, the heat on the surface of said substrate 10 is dissipated, So a master plate 65 having a fine pattern of protrusions 64 made of the catalyst metal is formed. By controlling the melting temperature and cooling rate, the width W of the protrusion 64 can be less than 50 nm, which cannot be achieved by conventional photolithography. Moreover, by controlling the spatial period T of the heat distribution 11, the protrusions 64 can form a fine interval L, which cannot be achieved by conventional photolithography.

Also, the master plate 65 having the pattern of the protrusions 64 can be formed by a dry method, so the improved method can obtain the advantages of easier growth, better reproducibility, and The cost is lower.

In addition, the heat distribution 11 is applied by diffracting the energy beam 12, so the spatial period T of the heat distribution 11 can be easily controlled by reducing the periodic interval P in the diffraction grating 13, thereby reducing the protrusion 64 The interval L between.

Moreover, in the improved method, at least the tip portion of the protrusion 64 is transferred onto the substrate 71 to be transferred, so one master 65 is used to transfer the protrusion 64 to many substrates to be transferred. On the transferred substrate 71, many substrates 74 are produced.

[Improvement method 5]

Then, referring to FIGS. 26-31 , the modified method 5 is described as follows. The improved method is the same as the improved method 4, except that in the melting step, the energy of the energy beam 12 is adjusted along the two-dimensional direction (that is, the X direction and the Y direction), so that the X direction heat distribution 31X and the Y direction A heat profile 31Y is applied to the surface of said substrate 10 . Therefore, the following description about the improved method 5 is simplified.

(melting step)

First, the melting step was performed as described in Modified Method 3. Here, the substrate 10 is made of iron (Fe) as a catalyst.

The material of the substrate 10 may be any material that can be used as a metal catalyst for carbon nanotube formation, and specific examples of the material of the substrate 10 are the same as those described as the second material in the first example.

(Protrusion forming step, Mother plate forming step)

Then, as in Modified Method 4, a bump forming step and a master plate forming step are performed. As shown in FIG. 26 , thereby, a master plate 82 having a pattern of protrusions 81 arranged two-dimensionally on the surface of the substrate 10 can be formed.

(transfer step)

Next, a transfer step is performed as described in Improved Method 4, and as shown in FIG. 27 , a substrate 84 is formed in which transfer patterns 83 made of catalyst metal (iron) are arranged two-dimensionally on the substrate to be transferred. on the surface of the substrate 71. This completes the catalyst alignment step.

(grow step)

Then, the growth step is carried out as described in the improved method 4. As shown in FIG. The nanotubes 85 are arranged in two-dimensional directions.

FIG. 29 is a photomicrograph (37.5 times magnification) of the carbon nanotube structure 86 formed on the substrate 84 through the above steps. The two-dimensionally distributed dotted white portions correspond to the growth of carbon nanotubes 85 on the substrate 84 by using a transfer pattern from the protrusions 81 of the master plate 82 as a catalyst.

Fig. 30 is a SEM (scanning electron microscope) photograph (50000 times magnification) depicting an area around the center of the white portion shown in Fig. 29 . As shown in FIG. 30 , it could be confirmed that the carbon nanotubes were grown in the white portion. Also, FIG. 31 is a SEM photograph (50,000 times magnification) depicting an area between a white portion and a black portion surrounding the white portion shown in FIG. 29 . As shown in FIG. 31 , it was confirmed that the carbon nanotubes were grown in the white portion; however, the carbon nanotubes were not observed in the black portion.

Therefore, in this improved method, the heat distribution 33 is formed by adjusting the energy magnitude of the energy beam 12 in the two-dimensional direction, thereby forming a master plate 82 having a pattern of the protrusions 81 arranged in a in the two-dimensional direction.

Also, in the improved method, when the tip portion of the protrusion 81 is transferred onto the substrate 71 to be transferred, the protrusion 81 is transferred to many substrates 71 to be transferred by using one master 82. On the transferred substrate 71, a plurality of substrates 84 are produced.

[Improvement method 6]

Next, referring to FIGS. 32A-34 , improvement method 6 is described as follows. The modified method further includes a coating layer forming step, wherein a coating layer made of a transfer material such as a catalyst metal is formed on the surface of the protrusion by the same method as described in the modified method 4 Formed on a substrate made of any material.

(melting step and protrusion forming step)

First, a substrate 90 made of, for example, silicon is prepared, and a melting step and a protrusion forming step are performed as in Improved Method 4 to form a master plate 92 having a pattern of protrusions 91 located on the substrate 90. on the surface.

(coating forming step)

Next, as shown in FIG. 32B , a coating layer 93 is formed on the surface of the protrusion 91 . In the modified method, the coating layer 93 is formed of iron (Fe) as a catalyst, and the coating layer 93 having a substantially uniform thickness is formed on the entire surface of the base material 90 including the protrusions 91; however, the The thickness of the coating layer 93 does not have to be uniform. The thickness of the coating 93 is determined by the height and size of the protrusions 91, and in the improved method, the thickness of the coating 93 is, for example, 5 nanometers. The coating layer 93 can be formed by, for example, vacuum deposition.

The transfer material as the material of the coating layer 93 may be any material usable as a metal catalyst for carbon nanotube formation, and specific examples of the transfer material are the same as those as the second material in the first example.

(transfer step)

Next, as shown in FIG. 33A , the protrusions 91 of the motherboard 92 and the conductive film 72 of the substrate 71 to be transferred are closely opposed to each other. At this time, in order to improve the transfer characteristics, it is preferable to apply pressure in the direction of the arrow A or perform heat treatment as in the improved method 4 .

Afterwards, when the mother plate 92 is pulled away from the substrate 71 to be treated, for example, as shown in FIG. (Fe) is transferred onto the substrate 71 to be transferred. Thus, a base material 95 having a transfer pattern 94 made of the same material as the coating layer 93 is formed. Thus, by using one master 92 to transfer said coating 93 onto many substrates 71 to be transferred, many substrates 95 are manufactured. When the coating layer 93 is worn out due to repeated transfer, the coating layer forming step may be repeated again to form another coating layer on the surface of the protrusion 91 . At this time, another coating layer may be formed after the remaining coating layer 93 is removed, or another coating layer may be formed on the remaining coating layer 93 .

Here, the meaning and specific examples of the "tip portion" are the same as those described in Modification 4 with reference to FIGS. 23 and 24 .

This completes the catalyst alignment step.

(grow step)

After the transfer coating 94 is formed on the substrate 71 to be transferred, for example, as shown in FIG. A nanotube structure 97 in which many carbon nanotubes 96 are arranged linearly.

Therefore, in the modified method, the coating layer 93 is formed on the surface of the protrusion 91, so only the coating layer 93 is made of the transfer material such as a metal catalyst. Accordingly, the base material 90 may be made of any material, the range of choices being extended according to the application.

Also, in the modified method, when the tip portion of the protrusion 91 coated with the coating 93 is transferred to the substrate 71 to be transferred, the coating 93 is transferred to the substrate 71 by using a master 92. Many substrates 71 to be transferred, thereby producing many substrates 95.

[Improvement method 7]

Next, referring to FIGS. 35A-35C , the modified method 7 is described as follows. In the improved method, the relative position between the master plate 65 and the substrate 71 to be transferred in the “transfer step” of the improved method 4 is changed, and the pattern of the master plate 65 is transferred to on the substrate 71 to be transferred.

First, as shown in FIG. 35A , as shown in Improved Method 4, referring to FIGS. 22A-22C , the first transfer is performed, and a first transfer pattern 101A is formed on the substrate 71 to be transferred.

Then, as shown in FIG. 35B , the relative position between the master 65 and the substrate 71 to be transferred is changed, for example, half of the interval L between the protrusions 64 to perform the second transfer. Afterwards, when the master plate is pulled away from the substrate 71 to be transferred, as shown in FIG. 35C, a second transfer pattern is formed in the middle position between the first transfer patterns 101A. 101B. Thus, a substrate 102 having a transfer pattern 101 including a first transfer pattern 101A and a second transfer pattern 101B is obtained.

In the improved method, the relative position between the master plate 65 and the substrate 71 to be transferred is changed, so as to transfer the pattern of the master plate 65 to the substrate 71 to be transferred multiple times, So many substrates 102 can be produced with finer patterns than in the first example.

In the improved method, the transfer is performed twice; however, the number of times of the transfer can be further increased. In this case, the relative position between the master 65 and the substrate 71 to be transferred may preferably be adjusted according to the number of transfers.

Also, in the modified method, the relative position between the master plate 65 and the substrate 71 to be transferred is changed, for example, half of the interval L between the protrusions 64 to perform the second transfer. , thereby forming the first transfer pattern 101A and the second transfer pattern 101B with a uniform interval; however, the interval between the first transfer pattern 101A and the second transfer pattern 101B does not have to be uniform .

[Improvement method 8]

Next, referring to Figs. 36A-37, the modified method 8 will be described as follows. In the improved method, a metal substrate made of a catalyst metal or the like is pressed onto a protrusion formed on the substrate to attach the catalyst metal to the tip of the protrusion, the substrate being Made from any material by modifying the same method described in Method 4.

(melting step and protrusion forming step)

First, a base material 110 made of, for example, silicon is prepared, and a melting step and a protrusion forming step are performed as described in Improved Method 4 to form a pattern of protrusions 111 located on the base material 110 as shown in FIG. 36A. On the surface.

(attach step)

Next, as shown in FIG. 36B, the protrusions 111 of the substrate 110 and the metal substrate 120 made of iron as a metal catalyst are closely opposed to each other. Therefore, as shown in FIG. 36C , iron constituting the metal base 120 is attached to the tip portion of the protrusion 111 to form a base 113 having an adhered pattern 112 made of the metal base 120. Made of the same material. At this time, in order to improve the adhesiveness, it is preferable to apply pressure or perform heat treatment as shown in Improved Method 4.

The material of the metal substrate 120 can be any material that can be used as a metal catalyst for forming carbon nanotubes. The specific example of the material of the metal substrate 120 is the same as the example of the second material described in the first example.

This completes the catalyst alignment step.

(grow step)

After forming the substrate 113 with the attachment pattern 112, for example, as shown in FIG. 37, carbon nanotubes 114 are grown on the substrate 113 by using the attachment pattern 112 as a catalyst, thereby forming a carbon nanotube structure 116, Many of the carbon nanotubes 114 are arranged linearly.

Therefore, in the improved method, the protrusion 111 and the metal substrate 120 are closely opposed to each other to form the attachment pattern 112 made of the same material as the metal substrate 120 located on the metal substrate 120. On the tip portion of the protrusion 111, it is easy to form the attachment pattern 112 made of the metal catalyst. Also, the material of the base material 110 can be selected arbitrarily, so the range of selection can be expanded according to the application.

Also, in the improved method, when the substrate 113 on which the attachment pattern 112 is formed is used as a master, to transfer the attachment pattern 112 attached to the tip portion of the protrusion 111 to the substrate to be transferred. When on the substrate 71, many substrates are formed by using one master to transfer the attachment pattern 112 onto many substrates 71 to be transferred.

[Improvement method 9]

Next, referring to FIGS. 38-40 , the modified method 9 is described as follows. The catalyst arrangement step in the improved method includes a "melting step", a "protrusion forming step" and a "planarizing step" for leveling the surface of the protrusions, the melting step including the The heat distribution 11 is applied to the surface of the substrate 10 to melt the surface of the substrate 10, and the "protrusion forming step" includes dissipating the heat on the surface of the substrate 10, corresponding to the heat Protrusions are formed at the locations of the distribution 11 (ie in a desired pattern). Afterwards, a "growth step" is performed to grow carbon nanotubes on the top surface of the planarized protrusions.

(melting step)

First, as shown in Improved Method 2, a melting step is performed. In the modified method, the substrate 10 is made of iron (Fe) as a metal catalyst.

The material of the substrate 10 may be any material that can be used as a metal catalyst for forming carbon nanotubes, and specific examples of the material of the substrate 10 are the same as the examples of the second material in the first example.

(Protrusion forming step)

In the melting step, when the irradiation of the energy beam 12 is stopped after the surface of the substrate 10 is melted, the surface temperature of the substrate 10 is gradually decreased to solidify the surface of the substrate 10 . At this time, when the energy of the energy beam 12 applied in the melting step exceeds a certain value, as shown in FIG. In the location of area 11H.

When the high temperature region 11H is linearly arranged in one-dimensional direction corresponding to the grooves 13A, the protrusions 134 are formed in a pattern of linear ribs (raised sides) arranged in one-dimensional direction. The width (line width) W of the protrusion 134 (ie, the size of the bottom end portion of the protrusion 134 in the modulation direction of the heat distribution 11 ) is determined by the melting temperature and the cooling rate. The melting temperature can be controlled by the energy of the energy beam 12 (that is, the number of pulse irradiations in the case of using an excimer laser), the higher the melting temperature, the more the width W of the protrusion 134 increases . The cooling rate can be controlled by a method of placing the substrate 10 or a fixture equipped with the substrate 10 in a vacuum, a method of gas flow, cooling in water or liquid nitrogen method, a method of heating and cooling slowly, the faster the cooling rate is, the more the width W of the protrusion 64 increases. In principle, the width W of the protrusion 134 can be any value larger than the atomic size of the material of the substrate 10, so, by controlling the melting rate and cooling temperature, the width W of the protrusion 134 can be less than 50 nanometers, This is beyond the reach of conventional photolithography.

The specific value of the width of the protrusion 134 is determined by the application of the substrate described below. For example, when carbon nanotubes are formed, the width W of the protrusion 134 is preferably in the range of 0.4 nm to less than 50 nm, more preferably 0.4-30 nm, and even more preferably 0.4-10 nm. The reason is related to Same reason as described in the first example.

Moreover, the interval L between the protrusions 134 (that is, the interval (pitch) between the protrusions 134 in the modulation direction of the heat distribution 11) is determined by the spatial period T of the heat distribution 11 (that is, the diffraction The periodic interval P of the grating 13 is determined by the wavelength λ) of the energy beam 12 . The shorter the wavelength λ, or the smaller the periodic interval P, the more the interval L between the protrusions 134 decreases, so the protrusions 134 with a fine interval L can be formed, which is a conventional photolithography method. unattainable. For example, the interval L between the protrusions 134 is preferably 100 nm or less, more preferably 50 nm or less, for the same reason as described in the first example.

(levelling step)

Next, as shown in FIG. 39A , a filling layer 136 is formed in the concave portion 135 surrounding the protrusion 134 . The filling layer 136 is used as a planarization layer in which the top surface of the protrusion 134 is planarized by the CMP described below, and the filling layer 136 is formed by coating, for example, silicon dioxide using SOG or CVD method. As the material of the filling layer 136, an insulating material (such as silicon nitride, polyimide, PMMA or a metal oxide film) or a semiconductor material (such as silicon or germanium) can be used instead of the above-mentioned silicon dioxide.

The filling layer 136 may be formed such that the protrusion 134 may be covered with the filling layer 136 or a portion of the protrusion 134 (eg, the tipmost portion of the protrusion 134 ) protrudes from the filling layer 136 .

Next, as shown in FIG. 39B , the protrusions 134 and the filling layer 136 may be polished by, for example, CMP to planarize the top surface 134A of the protrusion 134 and the top surface 136A of the filling layer 136 . This results in a substrate 137 comprising protrusions 134 having a planarized top surface 134A and a filling layer 136 covering the side surfaces of the protrusions 134, and the protrusions 134 The top surface 134A of is exposed from the filling layer.

The width Wa of the planarized top surface 134A can be controlled within a certain range, which can be obtained from the width W of the protrusion 134 through polishing time and CMP. In other words, the cross-sectional area of the protrusion 134 gradually decreases toward the tip, so the longer the polishing time is, the more the width Wa of the top surface 134A increases. The interval L between the protrusions 134 is the same before and after flattening.

Therefore, when the top surface 134A of the protrusion 134 is flat, the width Wa of the top surface 134A can be less than 50 nanometers, which is the same as the width W of the protrusion 134, which cannot be achieved by conventional photolithography. Therefore, variations in the area and shape of the top surface 134A can be reduced, and the height can be uniformed.

This completes the catalyst alignment step.

(grow step)

After planarizing the top surface 134A of the protrusion 134, for example, as shown in FIG. A carbon nanotube structure 139, in which many carbon nanotubes 138 are arranged linearly.

Therefore, in the improved method, the heat distribution 11 is applied to the surface of the substrate 10, and after melting the surface of the substrate 10, the surface of the substrate 10 dissipates heat to correspond to the heat The location of the distribution 11 forms a pattern of protrusions 134, and then, the top surface 134A of said protrusions 134 is planarized. Therefore, by controlling the melting temperature and cooling rate, the width W of the protrusion 134 and the width Wa of the top surface 134A can be smaller than 50 nm, which cannot be achieved by conventional photolithography. Moreover, by controlling the spatial period T of the heat distribution 11, the protrusions 134 can form a fine interval L, which cannot be achieved by conventional photolithography.

Also, the base material 137 having the pattern of the protrusions 134 can be formed by a dry method, so the improved method can obtain the advantages of easier production and better reproducibility, compared to the method using conventional photolithography, Production is lower.

In addition, the heat distribution 11 is applied by diffracting the energy beam 12, so the spatial period T of the heat distribution can be easily controlled by reducing the period interval P in the diffraction grating 13, thereby reducing the The interval L between the protrusions 134 .

Moreover, in the improved method, the top surface 134A of the protrusion 134 is flattened, so, the same as the width W of the protrusion 134, the width Wa of the top surface 134A can be less than 50 nanometers, which is What cannot be achieved by conventional photolithography, the area and shape variation of the top surface 134A can be reduced, and the height can be homogenized.

[Improvement method 10]

Next, the improved method 10 of the present invention is described as follows. The improved method also includes a top surface transfer step, which includes transferring the raised pattern of the base material 137 obtained in the improved method 9 to another substrate to be transferred by using the base material 137 as a master plate. on the substrate.

First, as shown in FIG. 41 , a transfer master 140 (hereinafter referred to as a master) having protrusions whose top surfaces are flattened is formed. Like the base material 137 in Modification Method 9, the master plate 140 is formed by performing a melting step, a protrusion forming step, and a planarization step. In other words, the protrusions 134 and the filling layer 136 are formed on the substrate 10 to planarize the top surfaces 134A of the protrusions and the top surface 136A of the filling layer 136 .

(top surface transfer step)

Next, as shown in FIG. 42A , prepare the same substrate 71 to be transferred as in the improved method 4, the top surface 134A of the protrusion 134 of the master 140 and the conductive film of the substrate 71 to be transferred. 72 are closely opposite each other. At this time, in order to improve the transfer characteristics, it is preferable to apply pressure in the direction of arrow A, if necessary. Also, heat treatment is preferably performed because the transfer characteristics can be improved again.

Afterwards, when the master plate 140 is pulled away from the substrate 71 to be transferred, as shown in FIG. 42B, the pattern of the top surface 134A of the protrusion 134 is transferred to the substrate 71 to be transferred superior. Accordingly, a base material 152 having a transfer pattern 151 made of iron is formed on the base material 71 to be transferred. Thus, by using one master 140 to transfer the top surfaces 134A of the protrusions 134 onto many substrates 71 to be transferred, many substrates 152 are produced. Also, through the planarization step, the area and shape variation of the top surface 134A of the protrusion 134 can be reduced, and the height is uniformed, so the area and shape variation of the transfer pattern 141 are reduced. This forms the fine transfer pattern 151 with high precision. Also, when the protrusions 134 are worn out due to repeated transfer, the shape of the top surface of the protrusions 134 can be restored as long as polishing is repeated in the planarization step.

This completes the catalyst alignment step.

(grow step)

The transfer pattern 151 is formed on the substrate 71 to be transferred. After the substrate 152 is formed, for example, as shown in FIG. On the substrate 152, a carbon nanotube structure 154 is formed, in which many carbon nanotubes 153 are arranged linearly. The carbon nanotube structure 154 formed on the conductive film 72 can be used as a field electron emission device.

Therefore, in the example, the top surface 134A of the protrusion 134 is transferred to the substrate 71 to be transferred, so, by using a master 140 to transfer the top surface 134A of the protrusion 134 to On a plurality of substrates 71 to be transferred, a plurality of substrates 152 are produced. Also, through the planarization step, the area and shape variation of the top surface 134A of the protrusion 134 is small and the height is uniformed, so the transfer pattern 151 with high precision can be formed.

[Improvement method 11]

Next, the improved method 10 is described as follows. In the modified method, as shown in Modified Method 9, after the protrusion pattern is formed on the surface of the substrate 10, a control layer that prevents the growth of the carbon nanotubes is formed on the protrusion except for the tipmost portion. on the outer surface. In other words, in the improved method, the catalyst arranging step includes a "melting step", a "protrusion forming step" and a "control layer forming step", and the melting step includes the A heat distribution 11 is applied to the surface of the substrate 10 to melt the surface of the substrate 10, and the protrusion forming step includes dissipating heat from the surface of the substrate 10 at a time corresponding to the heat distribution 11 The protrusions are formed in positions (ie, in a desired pattern), and the control layer forming step includes forming a control layer that prevents the growth of the carbon nanotubes on the surface of the protrusions except for the tipmost portion. Thereafter, a "growth step" of growing the carbon nanotubes on the tipmost portion of the protrusion, which is not covered with the control layer, is performed.

(melting step and protrusion forming step)

First, as shown in Modified Method 9, the melting step and the protrusion forming step are performed, and the protrusions 134 are formed on the surface of the substrate 10 as shown in FIG. 38 .

(Control layer formation step)

Next, as shown in FIG. 44, the control layer 161 is formed on the surface of the protrusion 134 except the tipmost portion 134B. In the following growth steps, the control layer 161 prevents the growth of the carbon nanotubes from the side surfaces of the protrusions 134, so as to limit the growth area of the carbon nanotubes. Silicon forms the control layer 161 . As the material of the control layer 161, it can be the same as the filling layer 136 in the improved method 9, and an insulating material (such as silicon nitride, polyimide, PMMA) or an insulating material (such as a metal oxide film), Or semiconductor materials such as silicon or germanium instead of silicon dioxide. In principle, when an insulating material is used as the material of the control layer 161, the area surrounding the tipmost portion 134B of the protrusion 134 is filled with the control layer 161 made of insulating material, so, compared to surrounding the carbon In the case of nanotubes without an insulator, higher electric fields can be concentrated on the carbon nanotubes.

This completes the catalyst arranging step, forming the substrate 162 in which the control layer 161 is formed on the surface of the protrusion 134 except the tipmost portion 134B.

(grow step)

After forming the base material 162, for example, as shown in FIG. 45, carbon nanotubes 163 are grown by using iron exposed as a catalyst to the tipmost portion 134B of the protrusion 134, thereby forming carbon nanotube structures 164, many of which Carbon nanotubes 163 are arranged linearly.

Therefore, in the improved method, the control layer 161 is formed on the surface of the protrusion 134 except the tipmost portion 134B, so the carbon nanotube 163 grows only at the tipmost portion of the protrusion 134 Section 134B on.

"Method of Manufacturing Field Electron Emission Device and Method of Manufacturing Display Unit"

[fifth example]

Next, referring to Figs. 46-49, a method of manufacturing a field electron emission device and a method of manufacturing a display unit according to a fifth example of the present invention will be described as follows. In the method of this example, a field electron emission device including a cathode using carbon nanotubes is formed, the method includes a "catalyst forming step" of having a catalytic function for carbon nanotubes by melting distribution and by growing the carbon nanotubes In the "cathode forming step" of forming the cathode, the melting is achieved by modulating the heat profile. By the "separation groove forming step" of forming separation grooves on the surface of the base material, the alignment of the metals in the catalyst alignment step is avoided, so that the resulting field electron emission device can be used as, for example, a cathode plate of an FED.

The catalyst alignment step is the same as that described in the first example, the catalyst alignment step includes a "melting step" and a "deposition step", the melting step including a heat profile that will be modulated according to the desired pattern 11 applied to the surface of the substrate 10 to melt the surface of the substrate 10, the step of depositing comprising dissipating heat from the surface of the substrate 10, depositing the second material at a temperature corresponding to the heat Distribute 11 positions (ie in the desired pattern). Also, the cathode forming step is basically the same as the growing step in the method of manufacturing tubular carbon molecules of the first example. Accordingly, the same elements are denoted by the same numerals as in the first example. Also, parts overlapping with the manufacturing steps in the first example can be described with reference to FIGS. 1-3.

(catalyst alignment step)

First, in a melting step, a modulated heat profile 11 is applied to said substrate 10 by the steps shown in FIG. 1 . Next, in the depositing step, the second material is deposited in a position corresponding to the high-temperature region 11H of the heat distribution 11 through the steps shown in FIG. 2 to form a substantially planar-shaped deposition region 14 . This completes the catalyst alignment step and forms the substrate 15 with the deposition area 14 on the substrate 10 .

(cathode forming step)

Then, through the steps shown in FIG. 3 , many carbon nanotubes 16 are grown on the substrate 15 by CVD. Thus, as shown in FIG. 46 , a cathode 170 in which the carbon nanotubes 16 are linearly arranged according to the pattern of the deposition region 14 is formed. The diameter of the carbon nanotubes 16 is determined by the type of carbon-containing compound used as a raw material and the growth environment. The smaller the number of carbon nanotubes 16 included in one cathode 170, the more preferable because it is easier to concentrate the electric field.

(Separation groove forming step)

Then, referring to FIGS. 47 and 48, the separation groove forming step will be described as follows. In the separation groove forming step, separation grooves are formed on the surface of the base material 15 to separate the cathodes 170 from each other.

First, as shown in FIG. 47, the energy beam 12 is diffracted by a diffraction grating 13 to form the heat distribution 11, which has a phase shift of 180° during the melting step, and the heat distribution 11 is applied to the substrate 15 on the surface. In other words, the relative position between the substrate 15 and the diffraction grating 13 is shifted from the position in the melting step by half the interval (pitch) between the arrays of carbon nanotubes 16 such that the high temperature of the heat distribution 11 A region 11H is formed at an intermediate position between the arrays of carbon nanotubes 16 .

The energy level of the energy beam 12 is set to cut (melt) the surface of the substrate 15 in the high temperature region 11H. Therefore, as shown in FIG. 48 , parallel partition grooves 180 are formed in the middle between the arrays of carbon nanotubes 16 to avoid the positions where carbon nanotubes 16 are formed. At this time, the position where the carbon nanotubes 16 are formed corresponds to the low temperature region 11L, so the energy level of the energy beam 12 is low, and the temperature of the carbon nanotubes 16 is limited to, for example, 400° C. or lower. Consequently, no adverse effects produced by the heat distribution 11 are exerted on the carbon nanotubes 16 .

The support body 10A is preferably made of an insulating material (such as silicon dioxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), plastic or glass. When the separation groove 180 is formed, the substrate 10 is completely cut, Because the cathodes 170 can be electrically separated from each other by the separation groove 180. And, it is preferable to form the separation groove 180 to be engaged in the support body 10A because the cathodes 170 can be electrically separated from each other more accurately. .

Therefore, a field electron emission device including the substrate 15, a plurality of cathodes 170 including carbon nanotubes 16, and separation grooves 180 formed on the substrate 15 to separate the cathodes 170 from each other can be obtained, the Carbon nanotubes 16 are arranged on the substrate 15 in a desired pattern. Each cathode 170 includes a linear array of carbon nanotubes 16 .

(FED)

Fig. 49 depicts a schematic diagram of a FED using the field electron emission device. In the FED, the cathode plate 200 and the anode plate 300 are combined into a unit facing each other, and the inside of the FED is in a high vacuum state.

The cathode plate 200 includes the base material 15 on which the above-mentioned cathode 170 is formed. As the cathode plate 200, a combination of many substrates 15 can be used depending on the size of the desired screen and the size of the substrate 15. The cathode 170 is connected to the data driver 220 through a cathode for red (R) 210R, a cathode for green (G) 210G, and a cathode for blue (B) 210B. As the cathode electrodes 210R, 210G, and 210B, the base material 10 cut from the separation groove 180 may be used, or other wiring may be arranged.

In the anode plate 300, anode electrodes for R 320R, anode electrodes for G 320G, and anode electrodes for B 320B are alternately arranged on a transparent base made of glass material or the like on the basis of pixels connected to pixels. Material 310 on. The anode electrodes 320R, 320G, and 320B are arranged orthogonally to the cathode electrodes 210R, 210G, and 210B, respectively. Also, a scan driver 340 is connected to the anode electrodes 320R, 320G, and 320B. A fluorescent film for R 330R, a fluorescent film for G 330G, and a fluorescent film for B 330B are respectively formed on the surfaces of the anodes 320R, 320G, and 320B on the side closer to the transparent substrate.

In the FED, for example, when a voltage is selectively applied between the anode electrodes 320R, 320G, and 320B and the cathode electrodes 210R, 210G, and 210B, field electron emission occurs in the cathode 170 located at the intersection point. , to emit electrons e ⁻ toward the anode electrodes 320R, 320G, and 320B. The electrons ^e- emitted from the cathode 170 pass through pores (not shown) distributed in the respective anode electrodes 320R, 320G, and 320B, and collide with the fluorescent films 330R, 330G, and 330B, thereby causing the fluorescent substances to emit light. . The light emitted by the fluorescent substance displays a desired image. In this case, the carbon nanotubes 16 of the cathode 170 are formed in the deposition area 14 made of iron deposited with a fine width W and a fine spacing L, which cannot be achieved by conventional photolithography. , so high-resolution images can be displayed clearly.

Thus, in this example, the patterning of said deposition areas 14 made of iron having a catalytic function for the formation of carbon nanotubes 16 is formed by melting, said melting being achieved by modulating the heat profile 11, The cathode 170 is formed by growing the carbon nanotubes 16 through the pattern of the deposition region 14, so by controlling the heat distribution 11, a deposition with a fine width W and a fine interval L that cannot be obtained by conventional photolithography can be formed The pattern of the region 14 is obtained, so that the cathode 170 is obtained, wherein the carbon nanotubes 16 are regularly arranged according to the pattern of the deposition region 14 . Therefore, a fine-pitch FED capable of clearly displaying a higher-definition pattern is obtained by using a field electron emission device including the cathode 170 .

Moreover, the substrate 15 having the pattern of the deposition area 14 can be formed by a dry method, so compared with the method using conventional photolithography, this example can obtain the following advantages, that is, easier production, better reproducibility, and lower cost.

Furthermore, in the example, the heat distribution 11 is applied to the surface of the substrate 10 made of silicon (including iron as an additive) so that after melting the surface of the substrate 10, the surface of the substrate 10 The surface dissipates heat, so that iron can be selectively deposited at locations corresponding to the heat distribution 11, forming a pattern made of deposition areas 14 of substantially planar shape.

In addition, in this example, the energy beam 12 is diffracted to apply the heat distribution 11, so when the period interval P in the diffraction grating 13 is reduced, the spatial period T of the heat distribution 11 can be easily Controlled, the interval L between the deposition regions 14 can be reduced to obtain high precision.

In addition, in this example, the separation groove 180 is formed on the surface of the substrate 15 to avoid (avoid) the carbon nanotubes 16, so the cathodes 170 are separated from each other by the separation groove 180, when When the cathodes 170 are used as the cathode plate 200 of the FED, the data driver 220 is connected to each cathode 170 to selectively apply a voltage.

Also, the heat distribution 11 can be applied by diffracting the energy beam 12 to form the separation groove 180, so the separation groove can be formed at an intermediate position between the carbon nanotube arrays 16, the The carbon nanotubes 16 can have fine intervals with high precision. Also, many separation grooves 180 can be formed in a shorter time than in the case of using conventional laser melting, and no adverse effect caused by heat is exerted on the carbon nanotubes 16 .

[Improvement method 12]

Next, referring to Fig. 50, the modified method 12 of the fifth example is described as follows. In the improved method, a separation groove 180 is formed for every multiple rows of carbon nanotubes 16 (for example, every two rows), and each multi-row cathode 170 includes two rows of carbon nanotubes 16 . Likewise, although not shown, every three or four columns of carbon nanotubes 16 may form a separation groove 180 .

When the spatial period of the heat distribution 410 applied to the surface of the substrate 15 is, for example, an integer multiple of the spatial period T of the heat distribution 11 in the melting step (nT; n is a positive integer, and n≥2), each Multiple columns may form the separation groove 180 . The spatial period can be controlled, for example, by setting the period interval of the diffraction grating 430 used in the separation groove forming step to an integer multiple of the period interval P of the diffraction grating in the melting step (nP; n is a positive integer, and n≥2). . Also, the spatial period is controlled by controlling the wavelength λ or the incident angle of the energy beam 12 .

The relative position between the substrate 15 and the diffraction grating 430 is controlled, so as in the first example, a high temperature region 410H of the heat distribution 410 is formed at the middle position between the rows of the carbon nanotubes 16 .

In the improved method, the separation grooves 180 are formed for each row of carbon nanotubes 16 .

[Improvement method 13]

Next, referring to Figs. 51-53, the improved method 13 of the present invention will be described as follows. In the improved method, after forming the pattern of the deposition region 14, a separation groove forming step is performed before forming the cathode 170 by growing the carbon nanotube 16.

(melting step and deposition step)

First, as described in the fifth example, a melting step and a deposition step are performed through the steps shown in FIGS. 1 and 2 to form a substrate 15 having a pattern of deposition regions 14 .

(Separation groove forming step)

Next, referring to FIGS. 51 and 52, the separation groove forming step will be described as follows. First, as shown in FIG. 51, the heat distribution 11 is applied to the surface of the substrate 15, the heat distribution is formed by diffracting the energy beam 12 through the diffraction grating 13, which has a 180° phase shift. In other words, the relative position of the substrate 15 and the diffraction grating 13 is shifted by half of the interval (pitch) between the deposition regions 14 from the position in the melting step, so that the high temperature region 11H of the heat distribution 11 is formed at The middle position of the deposition area 14 .

The energy level of the energy beam 12 is set so that the surface of the base material 15 is cut in the high temperature region 11H. Therefore, as shown in FIG. 52 , parallel separation grooves 180 are formed at intermediate points between the patterns of the deposition regions 14 to avoid the patterns of the deposition regions 14 .

(cathode forming step)

Next, as shown in FIG. 53 , the carbon nanotubes 16 are grown in the deposition region 14 through the steps shown in FIG. 3 to form the cathode 170 as in the fifth example.

In the improved method, after the separation groove 180 is formed, the cathode 170 is formed by growing the carbon nanotubes 16 , so it is sure to prevent the adverse effect of the heat distribution 11 from affecting the carbon nanotubes 16 .

[Improvement method 14]

FIG. 54 describes the separation groove forming step in the modified method 14 of the present invention. In the improved method, through the improved method 13, the same as the improved method 14, the separation groove 180 is formed every multiple deposition regions 14 (for example, every two deposition regions).

[Improvement method 15]

Figures 55-57 illustrate another modification of the fifth example. In the improved method, in the melting step of the fifth example, as shown in the improved method 1, the energy of the energy beam is adjusted in two-dimensional directions (namely, the X direction and the Y direction) to distribute heat in the X direction 81X and Y direction heat distribution 81Y is applied to the surface of the substrate 10 . In the improved method, the same numerals denote the same elements. Also, portions overlapping with the manufacturing portion in Modified Method 1 of the fifth example are described with reference to FIGS. 47 and 48 .

(catalyst alignment step)

First, as described in the improved method 1, a melting step is performed according to the steps shown in FIGS. 7-9 to apply the heat distribution 33 to the surface of the substrate 10 . Next, as shown in the improved method 1, a deposition step is performed in the steps described in FIGS. The position of the region 33H, thereby forming the deposition region 34 . Accordingly, a substrate 35 having a pattern of deposition areas 34 can be obtained.

(cathode forming step)

Then, as described in the improved method 1, as shown in FIG. 55 , the carbon nanotubes 36 are grown on the substrate 35 by, for example, the CVD method according to the steps shown in FIG. 12 to form the cathode 70 . The carbon nanotubes 36 are grown only on the deposition area 34, so the cathode 170 is formed in which the carbon nanotubes 36 are aligned in two-dimensional directions. The smaller the number of carbon nanotubes 36 included in one cathode 170 is, the more preferable because the electric field can be easily concentrated.

(Separation groove forming step)

Then, as described in the fifth example, a partition groove forming step was carried out in accordance with the steps shown in FIGS. 47 and 48 . Therefore, as shown in FIG. 56 , parallel partition grooves 180 are formed at intermediate positions to avoid carbon nanotubes 36 aligned in a two-dimensional direction.

Accordingly, a field electron emission device including a plurality of cathodes 170 each including a column of carbon nanotubes 36 arranged at certain intervals and a separation groove 180 separating the cathodes 170 is obtained.

(FED)

Fig. 57 is a schematic diagram of an FED using the field electron emission device. In the FED, the cathode plate 200 and the anode plate 300 are combined into a unit facing each other, and the inside of the FED is in a high vacuum state. The cathode plate 300 includes a substrate 35 on which the above-mentioned cathode 170 is formed. The structure of the anode plate 300 is the same as that of the fifth example.

In the FED, for example, when a voltage is selectively applied between the anode electrodes 320R, 320G, and 320B and the cathode electrodes 210R, 210G, and 210B, field electron emission occurs in the cathode 170 at the intersection, such that The fluorescent materials of the fluorescent films 330R, 330G, and 330B are made to emit light to display desired images. In this case, the carbon nanotubes 36 of the cathode 170 are two-dimensionally arranged at certain intervals, so the electric field intensity on the surface of each carbon nanotube 36 is increased to improve electron emission performance.

Therefore, in the improved method, as described in the improved method 1, the energy level of the energy beam 12 can be adjusted in the two-dimensional direction to form the heat distribution 33, so the pattern of the deposition regions 34 arranged in the two-dimensional direction can be formed on the surface of the substrate 10.

Moreover, as described in the improved method 1, the energy beam 12 is diffracted by the diffraction grating 32 to form a thermal distribution 33, so the spatial periods TX and TY of the thermal distribution 33 can be reduced by reducing the periodic interval in the diffraction grating 32. PX and PY are easily controlled so that the intervals LX and LY between the deposition regions 34 can be reduced.

[Improvement method 16]

FIG. 58 depicts the partition groove 180 formed in the partition groove forming step of the modified method 15 in a grid shape. In this case, in the separation groove 180, the interval in the X direction and the interval in the Y direction may be set separately.

When the partition grooves are formed in this mesh shape, in the cathode electrode serving as the cathode plate of the FED, wiring can be placed by forming holes from the back of the base material 35, for example.

Also, in addition to the modified method shown in FIG. 58, the partition groove forming step of modified method 15 may be variously changed. For example, after the deposition region 34 is formed, a separation groove forming step may be performed before forming the cathode 170 by growing carbon nanotubes 36 . Moreover, the separating groove 180 may be formed every multiple rows of carbon nanotubes (for example, every two rows).

[Sixth example]

Next, referring to FIGS. 59A to 62, a method of manufacturing a field electron emission device and a method of manufacturing a display unit according to a sixth example of the present invention will be described as follows. In the example, in the catalyst arrangement step, as described in Improved Method 2, the surface of the substrate 10 dissipates heat to form protrusions on the surface of the substrate 10, and the second material is deposited on The tip portion of the protrusion to form a substrate comprising a raised pattern, wherein at least the tip portion thereof is made of the second material. Also, in the example, in the cathode forming step, the substrate and the electrode are opposed to each other, and an electric field is applied between them to vertically grow carbon nanotubes at a low voltage. Except for them, the manufacturing method of this example is the same as that of the fifth example, so the same numerals as the fifth example denote the same elements. Also, portions overlapping with the manufacturing portion in Modified Method 2 can be described with reference to FIGS. 1 and 14-17, and portions overlapping with the manufacturing steps in the fifth example can be described with reference to FIGS. 47 and 48.

(catalyst alignment step)

First, as described in Improved Method 2, after the melting step is performed according to the steps shown in FIG. 1, the deposition step is performed according to the steps shown in FIGS. In the protrusion 41, a deposit region 42 made of iron is formed at least at the tip portion thereof.

(cathode forming step)

Then, referring to FIGS. 59A-60 , the cathode forming step will be described as follows. As shown in the improved method 2, through the steps shown in FIG. 17 , the carbon nanotubes 44 are grown on the substrate 43 by, for example, CVD or PECVD to form a cathode 170 (see FIG. 60 ). At this time, as shown in FIG. 59A, the base material 43 and the electrode 510 made of, for example, carbon (C) are opposed to each other, and a voltage is applied between them. As shown in FIG. 59B , when the protrusions are formed on the substrate 43 , the electric field is increased at the position of the protrusions 41 , and the carbon nanotubes 44 can grow vertically. Therefore, the growth direction of the carbon nanotubes 44 can be controlled in a uniform direction under low voltage. In the cathode 170 obtained in the above steps, the orientation of the carbon nanotubes 44 is high, so that when the cathode 170 is used as a cathode of the FED, the electron emission performance can be improved. In the grown carbon nanotubes 44, the second material 46 deposited in the deposition region 42, ie iron in this example, is included.

When the carbon nanotubes 44 are grown while applying an electric field, it is preferable to use the first material (for example, highly conductive material, such as silicon) constituting the substrate 10, and add phosphorus (P) to the silicon, for example.

(Separation groove forming step)

Next, as described in the fifth example, a partition groove forming step is performed through the steps shown in FIGS. 47 and 48 . Therefore, as shown in FIG. 61 , the separation groove 180 is formed in the middle between the rows of carbon nanotubes 44 to avoid the rows of carbon nanotubes 44 .

Therefore, it is possible to obtain a plurality of cathodes 170 each comprising a column of carbon nanotubes 44 arranged linearly and a separation groove 180 separating the cathodes 170 from each other.

(FED)

Fig. 62 depicts a schematic diagram of an FED using the field electron emission device. In the FED, the cathode plate 200 and the anode plate 300 are combined as a unit facing each other, and the inside of the FED is in a high vacuum state. The cathode plate 200 includes a base material 43 on which the above-mentioned cathode 170 is formed. The structure of the anode plate 300 is the same as that described in the first example.

In the FED, for example, when a voltage is selectively applied between the anode electrodes 320R, 320G, and 320B and the cathode electrodes 210R, 210G, and 210B, field electron emission occurs in the cathode 170 located at the intersection point. , the fluorescent substances in the fluorescent films 330R, 330G and 330B emit light to display desired images. In this case, the growth direction of the carbon nanotubes 44 of the cathode 170 is vertically aligned, and the orientation of the carbon nanotubes 44 is high, so the number of emitted electrons is average, thereby improving the The electron emission performance described above. Also, variations in strength can be prevented.

Therefore, in this example, the protrusion 41 (wherein at least the tip portion thereof is made of the second material (iron)) is formed at a predetermined position of the base material 10, so, compared to the pattern formed as In the case of the planar shape, the width of the deposition region 42 can be reduced, and a finer pattern can be formed compared to the fifth example.

Moreover, in this example, the substrate 43 and the electrode 510 are opposed to each other, and a voltage is applied between them, so the growth direction of the carbon nanotubes 44 can be controlled to a uniform direction under low voltage. Therefore, the orientation of the carbon nanotubes 44 of the cathode 170 can be improved, and when the cathode 170 can be used as a cathode of an FED, the electron emission performance can be improved and the intensity can be prevented from changing.

[Improvement method 17]

63A and 63B depict a modified method of the cathode forming step in the sixth example. In the improved method, as shown in FIG. 63A, two substrates 63 are opposed to each other, so that the patterns of the protrusions 41 of the two substrates 43 are opposed to each other, and the two substrates 43 are applied between the two substrates 43. electric field. In the modified method, the electric field is increased at the position of the protrusion 41, and as shown in FIG. 63B, the carbon nanotube 44 can be vertically grown from the tip portions of the protrusion 41 of the two substrates 43. Therefore, in addition to the effect in the sixth example, the carbon nanotubes 44 can be vertically formed on the two substrates 43 at the same time, so the production efficiency can be further improved.

[Improvement method 18]

Next, another modified method of the cathode forming step in the sixth example will be described as follows with reference to FIGS. 64-65B. In the improved method, the electrodes whose raised pattern corresponds to the pattern of the bumps 41 of the substrate 43 can be used as electrodes, and the substrate 43 and the electrodes are distributed so that the bumps 41 of the substrate 43 The pattern and the raised pattern of the electrode may then be opposed to each other.

First, as shown in FIG. 64, as described in the melting step and the deposition step in the sixth example, the pattern of the bumps 511 is formed on the same electrode 510 as described in the sixth example to form a bump electrode 512. The shape, width W, and interval L of the protrusions 511 are the same as those of the protrusions 41 except that no deposition area is formed at the tip portion of the protrusions 511 .

Next, as shown in FIG. 65A , the pattern of the protrusions 41 of the substrate 43 and the pattern of the protrusions 511 of the bump electrodes 512 are opposed to each other, and an electric field is applied between the substrate 43 and the bump electrodes 512. . Therefore, the electric field is increased in the positions of the protrusions 41 and 511, and as shown in FIG. 65B, the carbon nanotubes 44 can be vertically grown from the tip portions of the protrusions 41 of the substrate 43.

[Improvement method 19]

66A and 66B also illustrate another modified method of the cathode forming step in the sixth example. In the modified method, as shown in FIG. 66A, the substrate 15 (on which the pattern of the planar deposition region 14 in the fifth example is formed) and the bump electrode 512 (on which The patterns of the protrusions 511 described in the improved method 18) are opposed to each other, and an electric field is applied between them. Therefore, the electric field is increased in the position of the protrusion 511, and the carbon nanotube 16 can grow vertically from the position of the deposition region 14 as shown in FIG. 66B. In the grown carbon nanotubes 16, a second material deposited on said deposition area 14, namely iron in this example, is included.

[Improvement method 20]

Figures 67A and 67B depict a modification of the catalyst alignment step in the fifth example. In the improved method, the catalyst arranging step includes a "bump electrode forming step" and a "reduction/deposition step". A raised pattern is formed on the surface of the electrode, and the reduction/deposition step includes applying an electric field between the raised electrode and the conductive substrate in a solution containing a catalyst having a catalyst function, thereby forming a pattern corresponding to the conductive substrate on the conductive substrate. A pattern of raised electrodes (made of metals that function as catalysts) to reduce and deposit said metals.

(Protrusion electrode formation step)

As shown in FIG. 64 in Modified Method 18, the pattern of protrusions 511 is formed on the surface of an electrode 510 having a flat surface to form a protrusion electrode 511 . The method of forming the protrusion 511 is the same as the modified method 18 .

(reduction/deposition step)

Next, as shown in FIG. 67A, in a catalyst solution 520 including a metal (for example, iron) having a catalytic function for forming carbon nanotubes, the bump electrode 512 and the conductive substrate 530 may face each other, and between them Apply an electric field between them. As the metal having a catalyst function, the materials described as the second material in the first example can be used in addition to iron. Therefore, an electric field is raised at the position of the protrusion 511, and as shown in FIG. 67B, iron is deposited on the conductive substrate 530 according to the pattern of the protrusion 511 by reduction, thereby forming a deposition region 531. Accordingly, a substrate 530 having a pattern of deposition regions 531 can be obtained, thereby completing the catalyst alignment step.

In the improved method, the pattern of the protrusions 511 is formed on the surface of the planar electrode 510 by heat distribution, so that the pattern of the protrusions 511 is formed on the conductive substrate 530 by a catalyst. The deposition region 531 is made of metal (iron), so the deposition region 531 can be formed corresponding to the pattern of the protrusions 511, which has a fine width and a fine interval, which cannot be achieved by conventional photolithography.

[Seventh example]

Next, referring to Figs. 68A-70, the method of manufacturing the field electron emission device and the method of manufacturing the display unit in the seventh example will be described as follows. In the example, a drawing-out electrode forming step of forming a drawing-out electrode corresponding to the cathode may further be included. In other words, in the example, after the partition groove forming step was performed in the modified method 13, the lead-out electrodes were formed, and then carbon nanotubes were grown to form the cathode.

(melting step and deposition step)

First, as shown in FIG. 68A, as shown in the fifth example, the melting step and the deposition step are performed, and the substrate 15 including the pattern of the deposition region 14 is formed. As described above, the deposition region 14 is basically formed in a planar shape; however, for the purpose of easy understanding, in FIGS. 68A and 68B , the deposition region 14 protrudes from the surface of the substrate 15 .

(Separation groove forming step)

Next, as shown in FIG. 68B , a separation groove 180 is formed in the middle between the patterns of the deposition regions 14 to avoid the patterns of the deposition regions 14 . The method of forming the separation groove 180 is the same as that described with reference to FIGS. 51 and 52 in Modified Method 13. Referring to FIG.

(Extraction electrode formation step)

After the separation grooves 180 are formed, a lead electrode forming step is performed. First, as shown in FIG. 69A , an insulating film 611 made of, for example, silicon dioxide (SiO ₂ ) or the like is formed on the substrate by, for example, spin coating or chemical vapor deposition.

Next, as shown in FIG. 69B, a conductive film 612 made of, for example, niobium (Nb), molybdenum (Mo), or the like is formed on the insulating film 611 by, for example, spin coating or chemical vapor deposition.

After the conductive film 612 is formed, as shown in FIG. 69C , small hole portions 613 are formed corresponding to each deposition region 14 in the insulating layer 611 and the conductive film 612 by, for example, photolithography or reactive ion etching. Accordingly, a lead-out electrode 614 made of niobium or molybdenum is formed on the base material 15 with the insulating film 611 between the base material 15 and the lead-out electrode.

(cathode forming step)

Next, as shown in FIG. 70 , the carbon nanotubes 16 are grown in the deposition region 14 to form a cathode 170 as in the fifth example. Accordingly, a field electron emission device including the extraction electrode 614 corresponding to the cathode 170 can be obtained.

(FED)

Fig. 71 depicts a schematic diagram of a FED using the field electron emission device. In the FED, the cathode plate 200 and the anode plate 300 are combined as a unit facing each other, and the inside of the FED is in a high vacuum state.

The cathode plate 200 includes the above-mentioned cathode 170 and the substrate 15 on which the extraction electrode 614 corresponding to the cathode 170 is formed. The extraction electrodes 614 include extraction electrodes for R 614R, extraction electrodes for G 614G, and extraction electrodes for B 614B corresponding to the cathode electrodes 210R, 210G, and 210B, respectively. Extraction electrodes for R 614R, extraction electrodes for G 614G, and extraction electrodes for B 614B were connected to a scan driver (not shown).

The structure of the anode plate 300 is the same as that of the first example, except that a predetermined DC voltage is fixedly applied to the anode electrodes 320R, 320G, and 320B. In FIG. 71, only the anode electrode 320R and the fluorescent film 330R are depicted.

In the FED, for example, when a voltage is selectively applied between the extraction electrodes 614R, 614G, and 614B and the cathode electrodes 210R, 210G, and 210B, field electron emission occurs in the cathode 170 at the intersection point, The fluorescent substances (refer to FIG. 6 ) of the fluorescent films 330R, 330G, and 330B emit light to display desired patterns. In this case, the extraction electrode is formed corresponding to the cathode 170, so field electron emission occurs at a low voltage.

Therefore, in this example, the extraction electrode 614 is formed corresponding to the cathode 170, so the field electron emission occurs at a low voltage.

[Improvement method 21]

Next, referring to Figs. 72A-74, an improved method of the seventh example will be described as follows. In the modified method, in the seventh example, as described in the modified method 11, after forming a convex pattern on the surface of the substrate 10 (made of iron (Fe) as a metal catalyst), after A control layer capable of preventing the growth of the carbon nanotubes is formed on the surface of the protrusions other than the tipmost portion, and the same numerals denote the same elements. The overlapping portion with the manufacturing method in the fifth example can be described with reference to FIGS. 47 and 48, and the overlapping portion with the manufacturing method in the seventh example can be described with reference to FIGS. 69A-69C.

In other words, in the improved method, the catalyst arranging step includes a "melting step", a "protrusion forming step" and a "control layer forming step", and the melting step includes the A heat distribution 11 is applied to the surface of the substrate 10 to melt the surface of the substrate 10, and the protrusion forming step includes dissipating heat from the surface of the substrate 10 at a position corresponding to the heat distribution 11 (ie, in a desired pattern), the control layer forming step includes forming a control layer capable of preventing the growth of the carbon nanotubes on the surface of the protrusions except for the tipmost portion. A "separation groove forming step" of forming a separation groove may be performed, if necessary. After that, a "cathode formation step" is performed, that is, a cathode is formed by growing the carbon nanotubes at the tipmost portions of the protrusions not covered with the control layer.

(melting step and protrusion forming step)

First, as shown in Modified Method 11, a melting step and a protrusion forming step are performed, and a pattern of the protrusions 134 is formed on the surface of the substrate 10 as shown in FIG. 72A .

(Separation groove forming step)

After that, as described in the fifth example, as shown in FIG. 72B , the separation groove 180 is formed through the steps shown in FIGS. 47 and 48 .

(Control layer formation step)

Next, as described in Modified Method 11, as shown in FIG. 72C , a control layer 161 is formed on the surface of the protrusion 134 other than the tipmost portion 134B through the steps shown in FIG. 44 .

This completes the catalyst arranging step, and forms the substrate 700 in which the control layer 161 is formed on the surface of the protrusion 134 except for the tipmost portion.

(Extraction electrode formation step)

After the base material 700 is formed, as shown in the seventh example, the extraction electrode forming step is performed through the steps shown in FIGS. 69A-69C . In other words, first, as shown in FIG. 73A , an insulating film 611 made of, for example, silicon dioxide or the like is formed on the substrate 700 by, for example, sputtering or chemical vapor deposition.

Next, as shown in FIG. 73B , a conductive film 612 made of, for example, niobium (Nb), molybdenum, or the like is formed on the insulating film 611 by, for example, sputtering or chemical vapor deposition.

After the conductive film 612 is formed, as shown in FIG. 73C , small hole portions 612 are formed in the insulating film 611 and conductive film 612 corresponding to the tipmost portions 134B of the respective protrusions 134 by, for example, photolithography and reactive ion etching. Therefore, the extraction electrode 614 made of niobium or molybdenum is formed on the base material 700 with the insulating film 611 between the extraction electrode 614 and the base material 700 .

(cathode forming step)

Next, as shown in FIG. 74 , as described in Modified Method 11, the carbon nanotubes 163 are grown from the tipmost portions 134B of the respective protrusions 134 to form the cathode 710 . Accordingly, a field electron emission device including the extraction electrode 614 corresponding to the cathode 710 can be obtained.

Therefore, in the improved method, in addition to the effect of the seventh example, the control layer 161 is formed on the surface of the protrusion 134 except the tipmost portion 134B, so the carbon nanotube 163 can be grown only on the on the tipmost portion 134B of the protrusion 134 .

In particular, when an insulating material is used as the material of the control layer 161, the area around the tipmost portion 134B of the protrusion 134 is filled with the control layer 161 made of an insulating material, so compared to the carbon nanotube If there is no insulating material around the carbon nanotubes 163, a higher field intensity can be concentrated on the carbon nanotubes 163.

Although the present invention has been described with reference to the examples and modifications, the present invention is not limited to these examples and modifications, and many modifications are possible. For example, in the above examples, the energy level of the energy beam 12 can be adjusted by the number of pulsed irradiations; however, the number of pulsed irradiations, irradiation intensity and pulse width can be adjusted.

Also, in the above example and the above modified method, the heat distributions 11 and 41 are formed by using the diffraction gratings 13, 32, and 43; however, the heat distributions 11 and 41 may be formed by using a beam splitter and a mirror.

In addition, in the above-mentioned examples and modified methods, the energy beam 12 can be applied by an XeCl excimer laser; however, any laser other than the XeCl can also be used as long as it can be modulated to form the heat distribution, and a typical general-purpose laser can be used. Electric furnace (diffusion furnace) or any other method with lamp as heater for heating.

In addition, in the above-mentioned examples and improved methods, the heat dissipation in the deposition step or the protrusion formation step is performed by natural cooling at room temperature after the completion of the melting step; however, it can be shortened by forced cooling at a temperature lower than room temperature. The depositing step or the protrusion forming step.

In addition, for example, in the cathode forming step of the modified method 15, as described in the sixth example, the substrate 35 and an electrode (not shown) are opposed to each other, and a voltage can be applied between them.

In addition, for example, as a combination of the second example and the sixth example, when the height of the carbon nanotubes grown in the vertical direction is homogenized by applying an electric field between the substrate and the electrode, the shape of the carbon nanotubes and growth directions can be uniform, and when the carbon nanotubes are used in FEDs, the electric field emission performance can be improved again.

Also, for example, after the carbon nanotubes 16 are highly homogenized as described in the second example, a lead-out electrode made of niobium or molybdenum may be formed on the pinned layer 18 as described in the seventh example. In this case, the fixing layer 18 is preferably made of an insulating material.

In addition, for example, in the method of manufacturing a field electron emission device and the method of manufacturing a display unit, the case where the catalyst arranging step is performed as described in the improved method 1 can be referred to the case where the catalyst arranging step is performed as described in the improved method 2 Refer to the sixth example, and refer to the improved method 21 for the case where the catalyst arrangement step is as described in the improved method 11. However, the improved method of improving the catalyst arranging step described in Methods 3-10 can be applied to the method of manufacturing a field electron emission device and the method of manufacturing a display unit.

The method of distributing the metal having a catalyst function on the substrate is not limited to the above-mentioned examples and modified methods. For example, protrusions may be formed on a substrate made of catalyst metal, the top surfaces of which may be planarized.

In addition, in the above examples and improved methods, the carbon nanotubes are formed into tubular carbon molecules as described; however, the present invention is not limited to this case, it can be applied to the formation of carbon nano tentacles (nanohorn) or carbon nano Fiber condition.

As described above, in the method for producing the tubular carbon molecule of the present invention, the tubular carbon molecule can be grown by distributing a metal having a catalyst function for the formation of the tubular carbon molecule by melting, which is achieved by modulating the heat distribution, so that it can be obtained by Controlling the thermal distribution forms patterns with fine widths and fine intervals, which cannot be achieved by conventional photolithography, and results in tubular carbon molecules, which can be regularly arranged corresponding to the patterns.

In the method of manufacturing the recording device of the present invention, the tubular carbon molecule can be grown by distributing a metal having a catalyst function for forming the tubular carbon molecule by melting, the melting being achieved by modulating the heat distribution, the tip of the tubular carbon molecule forming In a predetermined plane, the tip is formed as an open tip, and then a magnetic material is inserted into the tip portion of the tubular carbon molecule from the open tip, forming a magnetic layer. Therefore, the magnetization length can be of small size, which cannot be achieved by conventional photolithography. Therefore, the recording density can be very high. Moreover, the magnetic layer is separated by tubular carbon molecules, so there is no magnetic layer effect in other adjacent tubular carbon molecules, the predetermined magnetization direction can be stably maintained for a long time, and the reliability of the recording device can be improved.

As described above, in the method of manufacturing the field electron emission device of the present invention, in the field electron emission device of the present invention, in the method of manufacturing the display unit of the present invention, or in the display unit of the present invention, the catalyst arranging step is included. and said cathode forming step, said catalyst arranging step comprising distributing a metal having a catalytic effect on tubular carbon molecules on said substrate by melting, said melting being achieved by modulating a heat profile, said cathode forming step comprising The cathode is formed by growing the tubular carbon molecules, so by controlling the heat distribution, the catalyst metal can be distributed in patterns of fine width and fine intervals (which cannot be achieved by conventional photolithography), and can The cathode was obtained in which tubular carbon molecules were regularly arranged corresponding to the pattern.

Claims (3)

1. method of making tubular carbon molecule, it comprises:

Catalyst alignment step, this step comprise by fusing arranges the metal that tubular carbon molecule is had catalyst function, and described fusing reaches by the modulation heat distribution;

The growth step of growth tubular carbon molecule,

It is characterized in that described catalyst alignment step comprises:

The fusing step, this step comprises the modulation heat distribution is applied on the substrate surface, to melt the surface of described base material, described base material is included in first material second material as additive, wherein said modulation heat distribution is to make that the energy beam diffraction applies so that periodically form high-temperature area and low-temperature region on the surface of described base material by diffraction grating, and described energy beam is the directional light with single wavelength and homophase; And

Deposition step, this step comprise by the heat radiation of described substrate surface is deposited on described second material in the position corresponding to described heat distribution,

Wherein, described second material is a kind of like this material, can be by described second material being joined in described first material fusing point that reduces described first material,

And wherein, described first material is semiconductor or metal, and described second material is the metal with catalyst function.

2. make the method for tubular carbon molecule according to claim 1, it is characterized in that in described deposition step,, described second material is deposited on the surface of described base material with flat shape by making the surface radiating of described base material.

3. make the method for tubular carbon molecule according to claim 1, it is characterized in that in described deposition step, form projection by the surface radiating that makes described base material on the surface of described base material, described second material is deposited on the tip portion of described projection at least.

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