JP2609602B2 - Electron emitting device and method of manufacturing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electron-emitting device and a method for manufacturing the same, and in particular, a nucleation density on a surface to be deposited is sufficiently higher than a material of the surface to be deposited, and The present invention relates to an electron-emitting device in which a dissimilar material fine enough to grow only a single nucleus is provided, and a crystal grown by the single nucleus grown on the dissimilar material is used as an electron-emitting portion, and a method of manufacturing the same.

[Prior art] Conventionally, hot cathode type electron-emitting devices have been widely used as an electron-emitting source. However, electron emission using a hot electrode has a problem that energy loss due to heating is large and preheating is required. Was.

In order to solve these problems, several cold-cathode-type electron-emitting devices have been proposed, and a field-effect-type electron emission device that locally generates a high electric field and emits electrons by field emission. There are elements.

FIG. 10 is a schematic partial cross-sectional view showing an example of the above-mentioned field-effect type electron-emitting device, and FIGS. 11 (A) to 11 (D) are schematic steps for explaining a manufacturing method thereof.

As shown in FIG. 10, a conical electrode 19 made of Mo (molybdenum) or the like is provided on a substrate 21 made of Si or the like, and an insulating layer 20 made of SiO ₂ or the like having an opening provided around the electrode 19 is formed. And
An extraction electrode 18 having an end formed near the conical point is provided thereon.

In the electron-emitting device having such a structure, when a voltage is applied between the base 21 and the extraction electrode 18, electrons are emitted from the peak having a strong electric field intensity.

 The electron-emitting device is manufactured by the following steps.

First, as shown in FIG. 11 (A), an insulating layer 20 such as a SiO ₂ oxide film is formed on a substrate 21 such as Si, a Mo layer 18 is formed by electron beam evaporation or the like, and a PMMA (poly) -Methyl-me
An electron beam resist such as thacrylate) is applied by spin coating. After patterning by irradiating an electron beam, the electron beam resist is partially removed with isopropyl alcohol or the like, and the Mo layer 18 is selectively etched to form a first opening 22. After the electron beam resist is completely removed, the insulating layer 20 is etched using hydrofluoric acid to form a second opening 23.

Next, as shown in FIG. 11 (B), while rotating the base body 21 about the rotation axis X, the base body 21 is inclined at a predetermined angle θ.
Al is deposited on the upper surface of the Mo layer 18 to form an Al layer 24. At this time, since Al is also deposited on the side surface of the Mo layer 18, the diameter of the first opening 22 can be arbitrarily reduced by controlling the deposition amount.

Next, as shown in FIG. 11 (C), Mo is vapor-deposited perpendicular to the substrate 21 by electron beam vapor deposition or the like. At this time
Since Mo is deposited not only on the Al layer 24 and the substrate 21 but also on the side surfaces of the Al layer 24, the diameter of the first opening 22 gradually decreases as the Mo layer 25 is stacked. Deposits (Mo) deposited on the substrate as the diameter of the first opening 22 decreases.
The electrode 19 having a substantially conical shape is formed on the base 21 because the deposition range of the substrate also becomes smaller.

Finally, as shown in FIG.
By removing the Al layer 24, an electron-emitting device having the substantially conical electrode 19 is formed.

[Problems to be Solved by the Invention] However, the above-mentioned conventional electron-emitting device has a conical shape, for example, the height, angle, and bottom diameter of the electrode are the size of the first opening, the thickness of the oxide film, The reproducibility is poor because it is determined by various manufacturing conditions such as the distance between the substrate and the evaporation source, and when forming the above-mentioned electron-emitting devices at the same time, there is a large conical variation. was there.

An object of the present invention is to provide a method for manufacturing an electron-emitting device in which the shape of an electrode having a pointed head serving as an electron-emitting portion is prevented from changing, and the performance thereof is improved.

[Means for Solving the Problems] An electron-emitting device according to the present invention includes: a base having a conductive material surface; an insulating layer having an opening provided on the base;
A dissimilar material having a nucleation density sufficiently higher than that of the material of the insulating layer and sufficiently fine enough to grow only a single nucleus is formed on the insulating layer. An electrode having a peak made of a crystal grown as an electrode, and an extraction electrode provided on the insulating layer and provided in the vicinity of the peak, and a conductive material surface exposed at the opening. The grown crystal is connected to the electrode having the pointed head.

According to the method for manufacturing an electron-emitting device of the present invention, a step of forming an insulating layer on a substrate having a surface of a conductive material, the insulating layer having a nucleation density sufficiently higher than the material of the insulating layer and a single nucleus Forming a dissimilar material fine enough to grow only the same; providing an opening in the insulating layer to expose a portion of the conductive material surface; and a single nucleus grown on the dissimilar material. A step of growing a crystal to form an electrode having a pointed tip, and growing a crystal on the conductive material surface exposed to the opening, and connecting the electrode to the electrode having the pointed tip. It is characterized by the following.

[Effect] In the electron-emitting device of the present invention, the electrode having the peak is electrically connected to the surface of the conductive material through the opening provided in the insulating layer. In addition, it is manufactured by being insulated, and the integration degree and the reliability of the connection are improved.

In the method of manufacturing an electron-emitting device according to the present invention, the connection between the electrode having the crystal peak and the conductive material surface is performed by depositing the crystal on the conductive material surface exposed to the opening provided in the insulating layer. The electrode is connected to an electrode having a peak of a crystal grown around a single nucleus formed in a fine dissimilar material, and the electrical connection is made in a simple process.

[Example] Hereinafter, an example of the present invention will be described in detail with reference to the drawings.

1 (A) to 1 (F) are schematic partial cross-sectional views for explaining manufacturing steps of a first embodiment of a method for manufacturing an electron-emitting device according to the present invention.

First, as shown in FIG. 1 (A), a substrate 1 made of a conductive material (including a semiconductor) such as Si is provided with an insulating material of SiO _2.
The insulating layer 2 is formed.

Next, as shown in FIG. 1B, a concave portion 3 is formed in the insulating layer 2 by photo etching or the like.

Next, as shown in FIG. 1C, the concave portions 3 of the insulating layer 2 are formed.
An opening 4 is provided on the bottom surface of.

Next, as shown in FIG. 1 (D), S
A nucleation base 5 which is a dissimilar material such as i, Si ₃ N ₄ is provided.

Next, as shown in FIG. 1 (E), a single crystal 6 of M ₀ , W, Si or the like is formed around a single nucleus formed on the nucleation base 5.
Grow. The details of the method for producing this single crystal will be described later. At the same time as growing the single crystal 6, a single crystal 7 is grown on the conductive material surface exposed in the opening 4.

Next, as shown in FIG. 1 (F), the single crystal 6 is grown, connected to the single crystal 7, and further grown to form the electrode 8 having a pointed tip.

Now, the material of the single crystal 6, the material of the nucleation base 5, and the base 1
Let K, L, M, and N be the adhesion coefficients of single crystal atoms of the conductive material and the material of the insulating layer 2, respectively, and K>L>M> N. In the case of a material having the relationship of M, a single crystal 6 grows first around a single nucleus formed on the nucleation base 5, and then a single crystal 7 grows from the opening 4. , The single crystal 6 grows while maintaining the conical peak of the single crystal,
Even after connection with the single crystal 7, the crystal grows while maintaining the shape of the pointed head.

However, the relationship of K>M>L> N holds, and if the conductive material of the base 1 is a material having the relationship of L <M, a single crystal will grow from the opening 4 first, so that nucleation It is difficult to form a single crystal 6 having a conical point with a single nucleus formed on the base 5 as a center. Therefore, in this case, it is necessary to suppress the growth of the single crystal 7. For example, the opening 4 is formed as a hole having a small diameter and the thickness of the insulating layer is increased to reach the exposed surface of the conductive material. This can be dealt with by reducing the amount of single crystal atoms or by filling the opening 4 with a resist until the single crystal 6 becomes a certain size, and then growing the single crystal 7. it can.

Finally, to form an electrode layer such as M ₀ on the insulating layer 2, the electrode layer by photolithography or the like, an opening 10 is formed on the cusp of the electrode 8, the extraction electrode serving electrode layer 9 Then, an electron-emitting device is manufactured.

Although the case where the crystal formed on the conductive material surface is a single crystal is described here, the present invention is not limited to a single crystal, and the present invention can be applied to a case where the crystal is a polycrystal or the like.

A feature of the electron-emitting device of the present invention manufactured by the manufacturing process described above is that an electrode having a pointed head and a conductive material surface are connected to each other through an opening provided in an insulating layer. Accordingly, it is an object of the present invention to improve the mounting density by integrating wirings and improve the reliability.

Further, as described in the above embodiment, the method for manufacturing an electron discharge element of the present invention exposes the connection between the electrode having the crystal peak and the conductive material surface to the opening provided in the insulating layer. A crystal is deposited on the surface of the conductive material, and is connected to an electrode having a peak of a crystal grown around a single nucleus formed in a fine dissimilar material. Without this, the electrical connection is made in a simple process.

Note that a heterogeneous material having a nucleation density sufficiently higher than that of the material of the insulating layer and sufficiently fine enough to grow only a single nucleus is formed in the insulating layer. The manufacturing method of growing a single crystal as the center is determined by conditions such as the insulating layer 2, the nucleation base 5, the material of the deposit, the deposition conditions, etc. Since the recess 3 and the opening 10 of the electrode layer 9 are formed independently of the dimensional accuracy, variations in the size can be suppressed.
Since it is determined by the positional accuracy, it can be manufactured at a desired position with high accuracy. As a result, a multi-type electron-emitting device having a plurality of electron-emitting ports at a fine pitch,
It can be manufactured uniformly.

In addition, the shape of the electron emitting portion at the pointed tip is formed uniformly and sharply, the electric field intensity is made uniform and strong, the variation in the range of the operation start voltage is suppressed, and the electron emission efficiency can be further improved.

Further, it is possible to form an electrode having a pointed tip by depositing a single crystal on an insulating layer on which a single crystal cannot be formed due to crystallinity or the like, thereby improving electrical insulation. The area can be easily made, the conductivity of the electrode having the pointed tip can be improved, and the electron emitting portion of the pointed tip can be made to have a crystal structure of a certain structure, thereby reducing the Schottky effect. And the electron emission efficiency can be improved.

Hereinafter, a single crystal growth method for growing a single crystal on the insulating layer will be described in detail.

First, a selective deposition method for selectively forming a deposition film on a surface to be deposited will be described. Selective deposition is a method of selectively depositing a thin film on a substrate using the difference between materials, such as surface energy, adhesion coefficient, desorption coefficient, and surface diffusion rate, which influence nucleation during the thin film formation process. It is a method of forming.

FIGS. 2A and 2B are explanatory diagrams of the selective deposition method.

First, as shown in FIG.
And a thin film 12 made of a material having the above factors different from each other is formed at a desired portion. Then, when a thin film made of an appropriate material is deposited under appropriate deposition conditions, as shown in FIG.
The phenomenon that the thin film 13 grows only on the thin film 12 but not on the substrate 11 can be caused. By utilizing this phenomenon, the thin film 13 formed in a self-aligned manner can be grown, and a conventional lithography process using a resist can be omitted.

Materials that can be deposited by such a selective formation method include, for example, SiO ₂ as the substrate 11, Si, GaAs, silicon nitride as the thin film 12, and Si, W, GaAs, InP as the thin film 13 to be deposited. .

FIG. 3 is a graph showing the change over time in the nucleation density of the surface on which SiO ₂ is deposited and the surface on which silicon nitride is deposited.

As the graph shows, shortly after the start of deposition, SiO ₂
The nucleation density above is saturated below 10 ³ cm ^-2 , and its value hardly changes after 20 minutes.

On the other hand, on silicon nitride (Si ₃ N ₄ ),
Once saturated at 0 ⁵ cm ^-2 , then it does not change for about 10 minutes,
After that, it increases rapidly. In this measurement example, Si
This shows a case in which Cl ₄ gas is diluted with H ₂ gas and deposited by the CVD method under the conditions of a pressure of 175 Torr and a temperature of 1000 ° C. S
A similar effect can be obtained by adjusting pressure, temperature, etc. using iH ₄ , SiH ₂ Cl ₂ , SiHCl ₃ , SiF ₄ or the like as a reaction gas. Also, vacuum deposition is possible.

In this case, nucleation on SiO ₂ is not a problem, but by adding HCl gas to the reaction gas, nucleation on SiO ₂ is further suppressed, and deposition of Si on SiO ₂ is completely eliminated. Can be

Such a phenomenon is largely due to the difference in the adsorption coefficient, desorption coefficient, surface diffusion coefficient, etc. of the material surface of SiO ₂ and silicon nitride with respect to Si, but SiO ₂ reacts by the Si atoms themselves and the vapor pressure is high. The generation of silicon oxide etches SiO ₂ itself, and the fact that such an etching phenomenon does not occur on silicon nitride is also considered to be a cause of selective deposition (T. Yoneha).
ra, S.Yoshioka, S.Miyazawa Journal of Applied Physic
s 53,6839,1982).

If SiO ₂ and silicon nitride are selected as the material of the surface to be deposited as described above and silicon is selected as the deposition material, a sufficiently large difference in nucleation density can be obtained as shown in the graph. Note that, here, SiO ₂ is desirable as the material of the surface to be deposited. However, the material is not limited to this, and a difference in nucleation density can be obtained even with SiO _X.

Of course, the invention is not limited to these materials, it is sufficient if 10 ² times or more in a density of nuclei as shown by the difference the graph of nucleation density, also deposited by a material exemplified later film Selective formation can be performed.

As another method of obtaining the difference in nucleation density, a region having excessive Si, N, or the like may be formed by locally implanting ions of Si, N, or the like on SiO ₂ .

Utilizing such a selective deposition method, a heterogeneous material having a nucleation density sufficiently higher than that of the surface to be deposited is formed fine enough so that only a single nucleus grows. The single crystal can be selectively grown only at the existing position.

Since the selective growth of the single crystal is determined by the electronic state of the surface on which the single crystal is to be deposited, in particular, the state of dangling bonds, a material having a low nucleation density (for example, SiO ₂ )
Does not need to be a bulk material, but may be formed only on the surface of any material, substrate, or the like to form the surface on which the above-described deposition is performed.

4 (A) to 4 (C) are process charts showing an example of a method for forming a single crystal. FIGS. 5 (A) and 5 (B) show the substrate in FIGS. 4 (A) and 4 (C). It is a perspective view of.

First, as shown in FIGS. 4 (A) and 5 (A), a thin film 15 having a low nucleation density is formed on a substrate 14 to enable selective deposition, and a thin film 15 having a high nucleation density is formed thereon. The dissimilar material 16 is formed thin enough by depositing the dissimilar material thinly and patterning it by linography or the like. However, the size, crystal structure and composition of the substrate 14 may be arbitrary, and may be a substrate on which a functional element is formed. Further, as described above, the different material 16 is a thin film of Si, N, or the like.
15 includes an altered region having excess Si, N, etc. formed by ion implantation.

Next, a single nucleus of thin film material is formed only in the dissimilar material 16 by appropriate deposition conditions. That is, different materials 16
Must be formed fine enough to form only a single nucleus. The size of the dissimilar material 16 depends on the type of the material, but may be several microns or less. Further, the nucleus grows while maintaining the single crystal structure, and becomes an island-like single crystal grain 17 as shown in FIG. 4 (B). In order to form island-like single crystal grains 17, as described above, it is necessary to determine conditions so that nucleation does not occur on the thin film 15 at all.

The island-shaped single crystal grains 17 are made of different materials while maintaining the single crystal structure.
Further growing around the center 16, a single crystal 17 a of a rotating body having a substantially conical point is obtained as shown in FIG.

The thin film 15, which is the material of the surface thus deposited, is
Since the substrate 14 is formed on the substrate 14, any material can be used for the substrate 14 serving as a support, and even if a functional element or the like is formed on the substrate 14, a single crystal can be easily formed thereon. Can be formed.

In the above embodiment, the material on the surface to be deposited is the thin film 15.
However, a single crystal may be similarly formed using a substrate made of a material having a low nucleation density that enables selective deposition.

6 (A) to 6 (C) are formation process diagrams showing another example of the single crystal formation method.

As shown in FIG. 6, by dissimilarly forming a different material 16 on a substrate 15 made of a material having a low nucleation density that enables selective deposition, a single unit is formed in the same manner as in the example shown in FIG. Crystals can be formed.

(Specific Example) Next, a specific method for forming the single crystal layer in the above example will be described.

SiO ₂ is used as the material of the surface on which the thin film 15 is deposited. Of course, a quartz substrate may be used, or a metal, a semiconductor, a magnetic material, a piezoelectric material, an insulator, etc.
An SiO ₂ layer may be formed on the substrate surface by using a vacuum evaporation method or the like. The material of the surface to be deposited is SiO ₂ is desirable, it may be one of changing the value of x as SiO _X.

A silicon nitride layer (here, a Si ₃ N ₄ layer) or a polycrystalline silicon layer is deposited as a dissimilar material on the SiO ₂ layer 15 formed in this manner by a low pressure vapor phase epitaxy method. Alternatively, a silicon nitride layer or a polycrystalline silicon layer is patterned by a lithography technique using an ion beam, and is patterned to several microns or less, preferably to about 1 μm.
The following minute dissimilar material 16 is formed.

Subsequently, HCl and H ₂ , SiH ₂ Cl ₂ , SiCl ₄ , SiHCl ₃ , SiF ₄
Alternatively, Si is selectively grown on the substrate 15 by using a mixed gas with SiH ₄ . The substrate temperature at that time is 700-1100
C, pressure is about 100 Torr.

In a few tens of minutes, a single crystal of silicon nitride or polycrystal silicon on SiO ₂
By growing the Si grains 17 under optimal growth conditions, a single crystal 17a having a size from the size of the above-mentioned dissimilar materials to about several tens μm or more is formed.

(Silicon nitride composition) In order to obtain a sufficient difference in nucleation density between the material on the surface to be deposited and the dissimilar material as described above, it is not limited to Si ₃ N ₄ , but silicon nitride. The composition may be changed.

In a plasma CVD method in which a SiN ₄ gas and an NH ₃ gas are decomposed in an RF plasma to form a silicon nitride film at a low temperature, SiH ₄ is used.
By changing the flow ratio of the ₄ gas and the NH ₃ gas, the composition ratio of Si and N of the silicon nitride film to be deposited can be changed greatly.

FIG. 7 is a graph showing the relationship between the flow ratio of SiH ₄ and NH ₃ and the composition ratio of Si and N in the formed silicon nitride film.

The deposition conditions at this time were an RF output of 175 W and a substrate temperature of 380 ° C., and the flow rate of NH ₃ gas was changed while the flow rate of SiH ₄ gas was fixed at 300 cc / min. As shown in the graph, when the gas flow ratio of NH ₃ / SiH ₄ was changed from 4 to 10, Si in the silicon nitride film was changed.
Auger electron spectroscopy revealed that the / N ratio varied from 1.1 to 0.58.

In addition, the composition of a silicon nitride film formed under a reduced pressure of 0.3 Torr and a temperature of about 800 ° C. by introducing a SiH ₂ Cl ₂ gas and an NH ₃ gas by a reduced pressure CVD method is almost stoichiometric. ₃ N ₄ (S
i / N = 0.75).

In addition, a silicon nitride film formed by heat-treating Si at about 1200 ° C. in ammonia or N ₂ (thermal nitriding method) has a closer stoichiometric ratio because the forming method is performed under thermal equilibrium. A composition can be obtained.

When nucleation density of the silicon nitride formed by various methods Si is grown nuclei of the Si used as the material of the surface to be higher deposition than SiO ₂ as described above, the difference in nucleation density by the composition ratio Occurs.

FIG. 8 is a graph showing the relationship between the Si / N composition ratio and the nucleation density. As shown in the graph, by changing the composition of the silicon nitride film, the nucleation density of Si grown thereon changes significantly. The nucleation conditions at this time were SiCl ₄
The gas is depressurized to 175 Torr and reacted with H ₂ at 1000 ° C. to generate Si.

Such a phenomenon that the nucleation density changes depending on the composition of silicon nitride affects the size of silicon nitride as a dissimilar material formed sufficiently finely to grow a single nucleus. That is, silicon nitride having a composition with a high nucleation density cannot form a single nucleus unless formed very finely.

Therefore, it is necessary to select the nucleation density and the optimal silicon nitride size from which a single nucleus can be selected. For example, under the deposition conditions to obtain a nucleation density of about 10 ⁵ cm ^−2, a single nucleus can be selected if the size of silicon nitride is about 4 μm or less.

(Formation of different types of materials by ion implantation) as a method for realizing nucleation density difference to Si, topically to SiO ₂ surface is a material of the surface to be low deposition of nucleation density Si, N, P, B, F, Ar, He, C, As, Ga, Ge, etc. are ion-implanted to form an altered region on the surface on which SiO ₂ is deposited, and this altered region is used as a material for the deposited surface having a high nucleation density. Is also good.

For example, often the SiO ₂ surface with a resist, exposing the desired portions, development, dissolved the SiO ₂ surface partially to expose it.

Subsequently, using SiF ₄ gas as a source gas, Si ions are implanted into the SiO ₂ surface at 10 keV at a density of 1 × 10 ¹⁶ to 1 × 10 ¹⁸ cm ⁻² . As a result, the projection range is 114 °, and the Si concentration on the SiO ₂ surface reaches 1010 ₂₂ cm ⁻³ . Since SiO ₂ is originally amorphous, the region into which Si ions are implanted is also amorphous.

In order to form the altered region, ion implantation can be performed by using a resist as a mask.However, using a focused ion beam technique, the silicon is narrowed down without using a resist mask.
Ions may be implanted into the SiO ₂ surface.

After performing the ion implantation in this manner, the resist is peeled off to form a deteriorated region where Si is excessive on the SiO ₂ surface. Si is vapor-phase-grown on the surface on which SiO ₂ is formed on which such altered regions are formed.

FIG. 9 is a graph showing the relationship between the implantation amount of Si ions and the nucleation density.

As shown in the graph, it can be seen that the nucleation density increases as the Si ⁺ implantation amount increases.

Therefore, by forming the altered region sufficiently fine,
Using this altered region as a dissimilar material, a single nucleus of Si can be grown, and a single crystal can be grown as described above.

It is to be noted that the formation of the altered region sufficiently fine enough to grow a single nucleus can be easily achieved by patterning a resist or narrowing a focused ion beam.

(Si deposition methods other than CVD) In order to grow single crystals by selective nucleation of Si, CV
In addition to the D method, a method in which Si is evaporated by an electron gun in a vacuum (<10 ⁻⁶ Torr) and deposited on a heated substrate is also used. In particular, MB that performs deposition in ultra-high vacuum (<10 ^-9 Torr)
In the E (Molecular Beam Epitaxy) method, it is known that a Si beam and SiO _{2 start} to react at a substrate temperature of 900 ° C. or higher, and there is no nucleation of Si on SiO ₂ (T.Yonehara, S. , Yos
hioka and S. Miyazawa Journal of Applied Physics 5
3, 10, p6839, 1983).

Utilizing this phenomenon, a single nucleus of Si is formed with perfect selectivity in minute silicon nitride scattered on SiO ₂ ,
Single crystal Si could be grown there. The deposition conditions at this time were as follows: vacuum degree 10 ⁻⁸ Torr or less, Si beam intensity 9.7 × 10
¹⁴ atoms / cm ² · sec, and the substrate temperature was 900 ° C. to 1000 ° C.

In this case, the reaction of SiO ₂ + Si → 2SiO ↑
Thus, a reaction product having a remarkably high vapor pressure is formed, and the SiO ₂ itself is etched by Si due to the evaporation.

On the other hand, a vapor etching phenomenon does not occur on silicon nitride, and nucleation and deposition occur.

Therefore, as the material of the surface to be deposited with a high nucleation density, tantalum oxide (Ta
The same effect can be obtained by using ₂ O ₅ ), silicon nitride oxide (SiON) or the like. That is, a single crystal can be similarly grown by minutely forming these materials to be the above-mentioned different materials.

(Growth of Tungsten Single Crystal) A case where tungsten is used as a material other than Si will be exemplified.

Tungsten, without causing nucleation on SiO _2, Si,
It is known that a polycrystalline film is deposited on WSi ₂ , PtSi, Al or the like. However, according to the crystal growth method of the present invention, a single crystal can be easily grown.

First, Si, WSi ₂ , PtSi, or Al is deposited on a glass, quartz, thermal oxide film, or the like containing SiO ₂ as a main component by vacuum evaporation, and is patterned by photolithography to a size of several μm or less.

Subsequently, it is installed in a reactor heated to 250 to 500 ° C,
WF ₆ gas and hydrogen gas mixed gas at a pressure of about 0.1 to 10 Torr
At a flow rate of 75 cc / min and 10 cc / min, respectively.

Thereby, tungsten is generated as represented by the reaction formula of WF ₆ + 3H ₂ → W + 6HF. At this time, the reaction between the tongue point and SiO ₂ is extremely low, and since no strong bonding occurs, nucleation does not occur, and thus no deposition occurs.

On the other hand, tungsten nuclei are formed on Si, WSi ₂ , PtSi, and Al, but since they are finely formed, only a single nucleus of tungsten is formed. Then, this single nucleus continues to grow and grows on SiO ₂ as a single crystal in the lateral direction. This is because the nucleus growth of tungsten does not occur on SiO ₂ , so that single crystal growth is not hindered and polycrystal is not formed.

The combination of the material of the surface to be deposited, the dissimilar material, and the deposition material described above is not limited to the combination shown in each of the above embodiments, and may be any combination of materials having a sufficient nucleation density difference. Is clear. Therefore, even in the case of a compound semiconductor such as GaAs or InP that can be selectively deposited, a single crystal or a group of single crystals can be formed by the present invention.

[Effects of the Invention] As described above in detail, according to the electron-emitting device of the present invention, the electrode having the pointed tip and the conductive material surface are electrically connected to each other through the opening provided in the insulating layer. This makes it possible to manufacture the electrode having the pointed head while electrically insulating the electrode, and to improve the integration degree and the reliability of the connection.

Further, according to the method for manufacturing an electron-emitting device of the present invention, the connection between the electrode having the single-crystal peak and the conductive material surface is simply performed on the conductive material surface exposed to the opening provided in the insulating layer. Crystals can be deposited and connected to an electrode having a single crystal peak that grows around a single nucleus formed in a fine dissimilar material, and electrical connection can be made in a simple process It becomes possible.

[Brief description of the drawings]

1 (A) to 1 (F) are schematic partial cross-sectional views for explaining a manufacturing process of an electron-emitting device according to a first embodiment of the manufacturing method of the present invention. FIGS. 2A and 2B are explanatory diagrams of the selective deposition method. FIG. 3 is a graph showing the change over time in the nucleation density of the surface on which SiO ₂ is deposited and the surface on which silicon nitride is deposited. 4 (A) to 4 (C) are formation process diagrams showing an example of a single crystal formation method. FIGS. 5 (A) and 5 (B) are perspective views of the substrate in FIGS. 4 (A) and 4 (C). 6 (A) to 6 (C) are formation process diagrams showing another example of the single crystal formation method. FIG. 7 is a graph showing the relationship between the flow ratio of SiH ₄ and NH ₃ and the composition ratio of Si and N in the formed silicon nitride film. FIG. 8 is a graph showing the relationship between the Si / N composition ratio and the nucleation density. FIG. 9 is a graph showing the relationship between the implantation amount of Si ions and the nucleation density. FIG. 10 is a schematic partial sectional view showing an example of a field-effect type electron-emitting device. 11 (A) to 11 (D) are schematic process diagrams for explaining the manufacturing method. DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Insulating layer 3 ... Concave part 4,10 ... Opening 5 ... Nucleation base 6,7 ... Single crystal 8 ... Electrode having a pointed head 9 ... Electrode layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuya Kaneko 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takeo Tsukamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Toshihiko Takeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takao Yonehara 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. ( 72) Inventor Takeshi Ichikawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-59-69495 (JP, A) JP-A-64-86428 (JP, A)

Claims (2)

(57) [Claims] 1. A substrate having a conductive material surface, an insulating layer having an opening provided on the substrate, and a single nucleus having a nucleation density sufficiently higher than that of the material of the insulating layer. An electrode having a pointed tip made of a crystal formed by growing a heterogeneous material fine enough to grow only the nucleus and centering on a single nucleus grown on the heterogeneous material; and an electrode provided on the insulating layer. And an extraction electrode provided in the vicinity of the pointed head, and a crystal grown on a conductive material surface exposed in the opening,
An electron-emitting device wherein the electrode having the pointed head is connected. 2. A step of forming an insulating layer on a substrate having a surface of a conductive material, wherein the insulating layer has a nucleation density sufficiently higher than that of the material of the insulating layer, and such that only a single nucleus grows. A step of forming a sufficiently fine dissimilar material, a step of providing an opening in the insulating layer to expose a part of the conductive material surface, and forming a crystal with a single nucleus grown on the dissimilar material as a center. Growing the electrode having a pointed tip, and growing the crystal on the surface of the conductive material exposed in the opening, and connecting to the electrode having the pointed tip.