JPS63207027A - Electron emitting element and its manufacture - Google Patents

Abstract

PURPOSE:To improve the property of electron emitting element as well as to prevent the variation of the form of an electrode with a spire to be an electron emitting part by connecting electrically the electrode with the spire and the surface of a conductive material through an aperture furnished at an insulating layer. CONSTITUTION:At first, an insulating layer 2 of an insulating material such as SiO2 is formed on a base body 1 made of a conductive material such as Si. And a recession 3 is formed at the insulating layer 2 by a hot etching or the like, and an aperture 4 is formed at the bottom surface of the recession 3. Moreover, a core forming base 5 for a different material such as Si or Si3 N4 is furnished at the bottom surface of the recession 3. Then a single crystal such as Mo, W, or Si is grown up around a single core formed on the core forming base 5. At the same time, a single crystal 7 is grown up on the conductive material surface exposed at the aperture 4. After that, the single crystal 6 is grown up to contact to the single crystal 7, and both are grown up further to form an electrode 8 with a spire. In such a way, the variation of the form of the electrode 8 is prevented, and an electron emitting element of an improved property can be manufactured.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an electron-emitting device and a method for manufacturing the same. The present invention relates to an electron-emitting device in which an electron-emitting portion is a crystal grown by a single nucleus grown in the foreign material, and a method for manufacturing the same.

[Prior art] Conventionally, hot cathode type electron emitting devices have been widely used as electron emission sources, but electron emission using a hot electrode has problems such as large energy loss due to heating and the need for preheating. 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 generates a locally high electric field within the device and emit electrons by field emission. There is an element.

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 (D) are schematic process diagrams for explaining the manufacturing method thereof. .

As shown in FIG. 10, a conical electrode 18 made of Mo (molybdenum) or the like is provided on a substrate 20 made of Si or the like.
An insulating layer 19 such as 5i02 is formed with an opening centered at 8, and an extraction electrode 17 whose end is 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 body 20 and the extraction electrode 17, electrons are emitted from the tip where the electric field strength is impaired.

The electron-emitting device described above is manufactured through the following steps.

First, as shown in FIG. 11(A), a base 20 such as SL
An insulating layer 1-9 such as an SiO2 oxide film is formed on the
An MO layer 17 is formed by electron beam evaporation or the like, and then P
MMA (poly-5etbyl-methacry
An electron beam resist such as (late) is applied using a spin code method. After patterning by irradiating an electron beam, the electron beam resist is partially removed using isopropyl alcohol, etc., and the MO layer 17 is selectively etched.
An opening 21 is formed.

After the electron beam resist is completely removed, the insulating layer 19 is etched using hydrofluoric acid to form the second opening 23.

Next, as shown in FIG. 11(B), while rotating the base body 20 about the rotation axis do. At this time, since AI is also deposited on the side surface of the Mo R 17, the diameter of the first opening 21 can be made arbitrarily small by controlling the amount of AI deposited.

Next, as shown in FIG. 11(C), Mo is deposited perpendicularly to the substrate 20 by electron beam evaporation or the like. At this time, the MO is not only on the A1 layer 23 and the base 20 but also on the A1 layer 23 and the base 20.
Since the MO layer 23 is also deposited on the sides, the diameter of the first opening 21 gradually becomes smaller as the MO layer 24 is stacked. Since the deposition range of the deposited material (MO) also becomes smaller, a substantially conical electrode 18 is formed on the base 20.

Finally, as shown in FIG. 11(D), the deposited MO layer 24 and AI layer 23 are removed to form an electron-emitting device having a substantially conical electrode 18.

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

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing an electron-emitting device that prevents variations in the shape of an electrode having a pointed portion serving as an electron-emitting portion and improves its performance.

[Means for Solving the Problems] The electron-emitting device of the present invention includes a substrate having a conductive material surface;
An insulating layer having an opening provided on the substrate, and a dissimilar material having a sufficiently higher nucleation density than the material of the insulating layer and sufficiently fine so that only a single nucleus grows in the insulating layer. an electrode having a tip of a crystal grown around a single nucleus grown in the dissimilar material, and an extraction electrode provided on the insulating layer and near the tip of the tip; The conductive material surface and the electrode having a pointed head are connected through the opening.

The method for manufacturing an electron-emitting device of the present invention includes the steps of forming an insulating layer on a substrate having a conductive material surface, and forming a single nucleus in this insulating layer with a sufficiently higher nucleation density than the material of the insulating layer. forming a dissimilar material fine enough to grow only a single nucleus grown in the dissimilar material; forming an opening in the insulating layer to expose a part of the surface of the conductive material; and a single nucleus grown in the dissimilar material. forming an electrode having a pointed head by growing a crystal around the opening, and growing a crystal on a surface of the conductive material exposed in the opening to connect it to the electrode having the pointed head. It is characterized by

[Function] The electron-emitting device of the present invention electrically connects the electrode having a pointed head to the conductive material surface through an opening provided in an insulating layer. This is to improve the density of planting and the reliability of the connection.

Further, in the method for manufacturing an electron-emitting device of the present invention, a connection between an electrode having a crystal tip and a conductive material surface is established by depositing a crystal on a conductive material surface exposed through an opening provided in an insulating layer. This method connects the peak of a crystal that grows around a single nucleus formed in a fine dissimilar material to an electrode that supports it, and allows electrical connection to be made through a simple process.

[Example] EMBODIMENT OF THE INVENTION Below, one embodiment of the present invention will be described in detail using the drawings.

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

First, as shown in FIG. 1(A), a conductive material such as Si (
5i0, which is an insulating material, is
An insulating layer 2 such as No. 2 is formed.

Next, as shown in FIG. 1(B), a recess 3 is formed in the insulating layer 2 by photoetching or the like.

Next, as shown in FIG. 1C, an opening 4 is provided at the bottom of the recess 3 of the insulating layer 2.

Next, as shown in Fig. 1 CD), the SL
A nucleation base 5 made of a different material such as , Si3N4 is provided.

Next, as shown in FIG. 1(E), Mo is formed around the single nucleus formed on the nucleation base 5.

A single crystal 6 of W, Si, etc. is grown. Note that details of the method for manufacturing this single crystal will be described later.

At the same time as this single crystal 6 is grown, a single crystal 7 is grown on the surface of the conductive material exposed in the opening 4.

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

Now, material for single crystal 6, material for nucleation base 5.

If the adhesion coefficients of single crystal atoms of the conductive material of the base 1 and the material of the insulating M2 are L, M, and N, then the relationship is K>L>M>N, and the conductive material of the base 1 is L. >M, the single crystal 6 will grow first around the single nucleus formed in the nucleation base 5, and then the single crystal 7 will grow from the opening 4. Therefore, the single crystal 6 grows while maintaining the conical point peculiar to a single crystal, and even after being connected to the single crystal 7, it grows while maintaining the shape of the point.

However, if the relationship is K>M>L>N and the conductive material of the base 1 is a material with the relationship L<M, then the single crystal will grow from the opening 4 first, so nucleation will occur. It is difficult to form a single crystal 6 having a conical point around a single core formed in the base 5.

Therefore, in this case, it is necessary to suppress the growth of the single crystal 7. For example, by making the opening 4 a micro-diameter hole and increasing the thickness of the insulating layer, it is necessary to suppress the growth of the single crystal 7 so that it reaches the exposed surface of the conductive material. Decreasing the amount of single crystal atoms or increasing the amount of single crystal 6
This can be solved by filling the opening 4 with resist until it reaches a certain size, and then growing the single crystal 7.

Finally, an electrode layer made of Mo or the like is formed on the insulating layer 2, and an opening 10 is formed on the tip of the electrode 8 by photolithography or the like to form an electrode layer 9 serving as an extraction electrode. In this way, an electron-emitting device is manufactured.

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

The electron-emitting device of the present invention manufactured by the manufacturing process described above is characterized in that an electrode having a pointed head and a conductive material surface are connected through an opening provided in an insulating layer.
By making it connect.

The goal is to integrate wiring to improve packaging density and improve reliability.

Furthermore, as described in the above embodiments, the method for manufacturing an electron-emitting device of the present invention involves exposing the connection between the electrode having the crystal tip and the conductive material surface through the opening provided in the insulating layer. A method in which crystals are deposited on the surface of a conductive material and connected to an electrode that has a tip of a crystal that grows around a single nucleus formed in a fine dissimilar material, and a process is specifically provided for the connection. This allows electrical connections to be made in a simple process without any hassle.

In addition, by forming a dissimilar material in the insulating layer that has a sufficiently higher nucleation density than the material of this insulating layer and which is sufficiently fine to the extent that only a single nucleus grows, the single nucleus grown in this dissimilar material is A manufacturing method in which a single crystal is grown as a center is such that an electrode 8 having a pointed head is formed on an insulating layer 2. which forms a deposition surface. Nucleation base5. It is determined by the material of the deposit, the deposition conditions, etc., and is formed independently of the dimensional accuracy of the opening 10 of the four parts 3 and the electrode layer 9. Since the position of the electrode 8 having a portion is determined by the positional accuracy of the nucleation base 5, it can be manufactured at a desired position with high precision. As a result, a multi-type electron-emitting device having a plurality of electron-emitting holes can be uniformly manufactured at a fine pitch.

In addition, by forming the shape of the electron emitting part at the tip to be uniform and sharp, the electric field strength can be made uniform and strong, and variations in the range of the operation start voltage can be suppressed, and the electron emission efficiency can be further improved. .

Furthermore, it is possible to deposit a single crystal on an insulating layer on which a single crystal cannot be formed on its surface due to crystallinity, etc., to form an electrode with a pointed head, which improves electrical insulation and greatly improves electrical insulation. It is possible to easily increase the area and improve the conductivity of an electrode having a pointed head, and it is also possible to form the electron emitting part of the pointed head into a crystal plane with a certain structure, thereby eliminating the Schottky effect. It is possible to improve the electron emission efficiency.

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

First, we will discuss the selective deposition method that selectively forms a deposited film on the deposition surface.The zero-selective deposition method is based on factors such as surface energy, adhesion coefficient, desorption coefficient, and surface diffusion rate that influence nucleation during the thin film formation process. Utilizing the differences in factors between materials,
This is a method of selectively forming a thin film on a substrate.

FIGS. 2(A) and 2(B) are illustrations of the selective deposition method.

First, as shown in FIG.
A thin film 12 made of a material having a different factor from 1 to 1 is formed at a desired portion. Then, when a thin film made of an appropriate material is deposited under appropriate deposition conditions, a phenomenon occurs in which the thin film 13 grows only on the thin film lz and does not grow on the substrate 11, as shown in FIG. can be caused. By utilizing this phenomenon, it is possible to grow a thin film 13 formed in a self-aligned manner, and it becomes possible to use a conventional resist or to omit a conventional resist.

Materials that can be deposited by such a selective formation method include, for example, SiO2 for the substrate 11, and a thin film 1 for the substrate 11.
2 is Si, GaAs, silicon nitride, and the thin film 13 to be deposited is St, W, GaAs, InP.
etc.

FIG. 3 is a graph showing changes over time in the nucleation density of the SiO2 deposition surface and the silicon nitride deposition surface.

As the graph shows, shortly after starting the deposition (Si0
The nucleation density on 2 is saturated below 103 cm,
The value hardly changes even after 20 minutes.

On the other hand, on silicon nitride (Si3 N4), it once saturates at ~4 x 105 cm-2, does not change much for 10 minutes, but increases rapidly after that.

In this measurement example, Sic 14 gas was diluted with H2 gas, the pressure was 175 Torr, and the temperature was 175 Torr. This shows the case where the film was deposited by the GVD method under conditions of 000°C. Also SiH4, SiH2012, 5iHC13, SiF4
A similar effect can be obtained by using the same as the reaction gas and adjusting the pressure, temperature, etc. Vacuum deposition is also possible.

In this case, nucleation on SiOz is hardly a problem, but by adding HGI gas to the reaction gas, SiOz
Nucleation on SiO2 can be further suppressed, and Si deposition on SiOz can be completely eliminated.

This phenomenon is largely due to the difference in adsorption coefficient, desorption coefficient, surface diffusion coefficient, etc. for Si on the material surface of 5i02 and silicon nitride, but Si02 reacts with the Si atoms themselves, and silicon monoxide, which has a high vapor pressure, The fact that Si02 itself is etched due to the formation of etching, and such an etching phenomenon does not occur on silicon nitride is thought to be a cause of selective deposition (T, Yonehara, S, Yoshiaka).
, S, former yazava Journal of Appl
ied Physics 53. [1839, 198
2).

In this way, by selecting Sjo 213 and silicon nitride as the materials of the deposition surface and selecting silicon as the deposition material, a sufficiently large difference in nucleation density can be obtained as shown in the graph. Note that although SiO2 is preferable as the material for the deposition surface here, the material is not limited to this, and a difference in nucleation density can be obtained even with SiOx.

Of course, the material is not limited to these materials, and it is sufficient if the difference in nucleation density is 102 times or more in terms of the density of nuclei, as shown in the same graph, and even with materials such as those exemplified in vk, the deposited film sufficient selection formation can be performed.

Another method for obtaining this difference in nucleation density is to locally implant ions of Si, N, etc. onto Si02 to
You may also form a region having the following.

By using such a selective deposition method and forming a foreign material with a nucleation density sufficiently higher than that of the material on the deposition surface in a sufficiently fine structure so that only a single nucleus grows, the presence of the fine foreign material can be reduced. It is possible to selectively grow single crystals only in certain locations.

The selective growth of single crystals depends on the electronic state on the surface of the deposition surface,
In particular, since it is determined by the state of dangling bonds, a material with a low nucleation density (e.g. Si02) does not have to be a bulk material, but can be formed only on the surface of any material or substrate to form the above-mentioned deposition surface. All you have to do is do it.

FIGS. 4(A) to 4(C) are formation process diagrams showing an example of a method for forming a single crystal, and FIGS.
It is a perspective view of the board|substrate in figures (A) and (C).

First, as shown in FIG. 4(A) and FIG. 5(A),
A thin film 15 with a low nucleation density that enables selective deposition is formed on the substrate 14, a different material 16 with a high nucleation density is thinly deposited on the thin film 15, and the different material 16 is made sufficiently fine by patterning by lithography or the like. to form. However, the size, crystal structure, and composition of the substrate 14 may be arbitrary, and it may be a substrate on which a single functional element is formed.

Further, as described above, the foreign material 16 refers to excessive Si, N, etc. formed by ion-implanting Si, N, etc. into the thin film 15.
It shall also include altered areas with etc.

A single core of thin film material is then formed in only the dissimilar material 16 by suitable deposition conditions. That is, the different material 16
must be formed sufficiently finely so that only a single nucleus is formed. The size of the different material 16 varies depending on the type of material, but may be several microns or less.
The nucleus grows while maintaining the single crystal structure, and becomes an island-shaped single crystal grain 17 as shown in FIG. 4(B). Island-shaped single crystal grain 1
7, the thin film 1 must be formed as described above.
It is necessary to determine conditions such that no nucleation occurs on 5.

The island-shaped single-crystal grains 17 further grow around the different material 16 while maintaining the single-crystal structure, and become a rotating single-crystal 17a having a substantially conical pointed head, as shown in FIG. .

Since the thin film 15, which is the material of the deposition surface, is formed on the substrate 14, any material can be used for the substrate 14, which serves as a support, and furthermore, functional elements etc. can be formed on the substrate 14. single crystals can be easily formed thereon.

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

FIGS. 6(A) to 6(C) are forming process diagrams showing other examples of the single crystal forming method.

As shown in the figure, by forming a sufficiently small dissimilar material 16 on a substrate 15 made of a material with a low nucleation density to enable selective deposition, it is possible to Can form crystals.

(Specific Example) Next, we will explain the specific method for forming the single crystal layer in the above example.
Do 1.

5i02 is used as the deposition surface material of the thin film 15. Of course, a quartz substrate may be used, and metals, semiconductors, magnetic materials, piezoelectric materials,
Sputtering method, CVD method,
A Si02 layer may be formed on the substrate surface using a vacuum evaporation method or the like.Although Si02 is preferable as the material for the deposition surface, it may be SiOx with a different value of X.

A silicon nitride layer (here, Si3 N 4 layer) is formed on the SiO2 layer 15 thus formed by low pressure vapor phase epitaxy.
Alternatively, a polycrystalline silicon layer is deposited as a different material, and the silicon nitride layer or polycrystalline silicon layer is patterned by a normal phosphorography technique or a phosphorography technique using X-rays, electron beams, or ion beams, preferably to a thickness of several microns or less. forms a minute dissimilar material 16 of ~IILm or less.

Next, HCI, H2, SiH2G+2, 5iC
14. Selectively grow Si on the substrate 15 using a mixed gas of SiH013, SiF4, or SiH4. At that time, the substrate temperature was 700 to 1100'', and the pressure was about 100 Torr.

In a period of about several tens of minutes, single-crystal Si grains 17 grow around a fine foreign material 16 of silicon nitride or polycrystalline silicon on Si02, and by setting the optimal growth conditions, the size of the grains can be increased. A single crystal 17a having a size ranging from about the size of the above-mentioned dissimilar material to about several tens of ILm or more is formed.

(Composition of silicon nitride) In order to obtain a sufficient nucleation density difference between the deposited surface material and the different material as described above, it is not limited to Si3N4, but the composition of silicon nitride can be changed. It may also be something you have.

Plasma CV that decomposes SiH4 gas and NH3 gas in RF plasma to form a silicon nitride film at low temperature
In method D, by changing the flow rate ratio of SiH4 gas and NH3 gas, the composition ratio of Si and N in the deposited silicon nitride film can be changed significantly.

FIG. 7 is a graph showing the relationship between the flow rate ratio of SiH4 and NH3 and the composition ratio of Si and N in the formed silicon nitride film.

The deposition conditions at this time were: RF output 175W, substrate temperature 38W.
The temperature was 0° C., the flow rate of SiH4 gas was fixed at 300 cc/min, and the flow rate of NH3 gas was varied. As shown in the same graph, the gas flow rate ratio of N H3/S i H4 is changed from 4 to
When changed to lO, S i / in the silicon nitride film
Auger electron spectroscopy revealed that the N ratio varied from 1.1 to 0.58.

In addition, low pressure CVD method test SiH2012i
The composition of the silicon nitride film formed under reduced pressure of 0.3 Torr and at a temperature of approximately 800°C is as follows:
Si3N4 (Si/N
-0.75).

In addition, Si was heated to about 1200°C in ammonia or N2.
A silicon nitride film formed by heat treatment (thermal nitriding method) can have a composition closer to the stoichiometric ratio because the formation method is carried out under thermal equilibrium.

When silicon nitride formed by the various methods described above is used as a deposition surface material with a Si nucleation density higher than 5i02 to grow the Si nuclei, a difference occurs in the nucleation density depending on the composition ratio.

FIG. 8 is a graph showing the relationship between the Si/N composition ratio and the nucleation density. As shown in the same graph, by changing the composition of the silicon nitride film, S
The nucleation density of i varies significantly. The nucleation conditions at this time were to reduce the pressure of 5iG14 gas to 175 Tart, and to
It is made to react with oo°C-t'H2 to generate St.

This phenomenon in which the nucleation density changes depending on the composition of silicon nitride affects the size of silicon nitride as a heterogeneous material that is formed finely enough to grow a single nucleus. That is, silicon nitride having a composition with a high nucleation density cannot form a single nucleus unless it is formed very finely.

Therefore, it is necessary to select the nucleation density and the optimum silicon nitride size for selecting a single nucleus. For example, for deposition conditions that yield a nucleation density of ˜10 5 cm −2 , a single nucleation can be selected if the silicon nitride size is about 4 uLm or less.

(Formation of different materials by ion implantation) As a method to realize a difference in nucleation density for St, Sf, N, P, B, F, Ar.

5i0 by ion implantation of He, C, As, Ga, Ge, etc.
An altered region may be formed on the deposition surface of No. 2, and this altered region may be used as the deposition surface material with a high nucleation density.

For example, the 5i02 surface is partially exposed by exposing, developing, and dissolving a desired portion of the resist on the 5i02 surface.

Subsequently, using S i F4 gas as a source gas, S
1Okev of i-ion is 1×1oIG~1×1018c
m-2c7) Density - tss The projected range for hitting the i02 surface is 114 people, and on the 5i02 surface, 51 g 1 degree reaches ~1022 cm-3.

Since S i 02 is originally amorphous, the region into which Si ions are implanted is also amorphous.

Note that to form the altered region, ion implantation can be performed using a resist as a mask, but focused ion beam technology can be used to form a narrowed S without using a resist mask.
i ions may be implanted into the 5i02 surface.

After performing the ion implantation in this manner, by peeling off the resist, an altered region containing excess Si is formed on the Si02 surface. St is grown in a vapor phase on the 5i02 sedimentation surface 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 same graph, it can be seen that the higher the Si content, the higher the nucleation density.

Therefore, by forming the altered region sufficiently finely, a single nucleus of Si can be grown using the altered region as a different material, and a single crystal can be grown as described above.

Note that forming the altered region sufficiently finely so that a single nucleus grows can be easily achieved by patterning a resist or narrowing down a focused ion beam.

(St deposition method other than CVD) To grow a single crystal by selective nucleation of Si, C
In addition to the VD method, Si is processed in vacuum (< 10-6To
A method in which the material is evaporated using an electron gun and deposited on a heated substrate is also used. In particular, in ultra-high vacuum (<10-
MB E (Nolecul
In the ar beam epitaxy) method, the substrate temperature is 9
At temperatures above 00°C, the Si beam and 5i02 begin to react, and S
It is known that Si nucleation on i02 is completely eliminated (T, Yonehara, S, Yoshioka
andS, Miyazawa Journal of
Applied Physics 53°10, p8
839, 1983).

Utilizing this phenomenon, we were able to form a single Si nucleus with perfect selectivity in minute silicon nitride dotted on SiO2, and grow single crystal St there.

The deposition conditions at this time were a vacuum level of 10-8↑orr or less, S
T-beam intensity 9.7×1014 atoma/+, s
" a sec, and the substrate temperature was 900°C to 1000°C.

In this case, due to the reaction 5i02 +Si→2SiO↑, a reaction product called SiO having a significantly high vapor pressure is formed, and this evaporation causes etching of 5to2 itself by Si.

On the other hand, on silicon nitride, the above-mentioned etching phenomenon does not occur, but nucleation and deposition occur.

Therefore, in addition to silicon nitride, tantalum oxide (Ta 205 ) can be used as a deposition surface material with a high nucleation density.
, silicon nitride oxide (SiOM), etc. can also be used to obtain similar effects. That is, by micro-forming these materials to form the above-mentioned dissimilar materials, a single crystal can be similarly grown.

(Tungsten single crystal growth) The case of tungsten as a material other than St will be exemplified.

Tungsten does not nucleate on Si02,
Si, WSi 2 , PtSi; It is known that a polycrystalline film is deposited on A1, etc. However, according to the crystal growth method according to the present invention, a single crystal can be easily grown.

First, on glass, quartz, thermal oxide film, etc. whose main component is Si02, WSi2, PtSi, or AI is deposited by vacuum evaporation, and several grams are deposited by photolithography.
Butter it to a size no larger than m.

Next, it is placed in a reactor heated to 250 to 500°C, and a mixed gas of wF6 gas and hydrogen gas is brought to a pressure of 0.
．． 75cc/win each under reduced pressure of 1-10↑orr
and flow at a flow rate of 10 CC/in.

As a result, tungsten is generated as expressed by the reaction formula -F6+3H2→-+8HF. At this time, the reactivity between tungsten and 5i02 is extremely low and no solid bond is formed, so nucleation does not occur and therefore no deposition occurs.

In contrast, Si%WSi 2 , PtSi, A
A tungsten nucleus is formed on I, but since it is formed finely, only a single tungsten nucleus is formed. This single nucleus then continues to grow until 5i02
It also grows horizontally as a single crystal. This is 5i0
This is because tungsten nuclei do not grow on No. 2, and therefore do not inhibit single crystal growth and become polycrystalline.

It should be noted that the combinations of the deposition surface material, different materials, and deposition materials described so far are not limited to those shown in each of the above examples, but it is clear that any combination of materials having a sufficient difference in nucleation density may be used. be.

Therefore, even in the case of a compound semiconductor such as GaAg or InP that can be selectively deposited, a single crystal or a group of single crystals can be formed according to the present invention.

[Effect of the Invention 1] As explained in detail above, according to the electron-emitting device of the present invention, the electrode having the pointed head and the conductive material surface are electrically connected through the opening provided in the insulating layer. By doing so, it is possible to manufacture an electrode having a pointed head in an electrically insulated manner, and to improve the degree of integration and connection reliability.

Further, according to the method for manufacturing an electron-emitting device of the present invention, the connection between the electrode having a single crystal peak and the conductive material surface is simply made on the conductive material surface exposed through the opening provided in the insulating layer. A crystal can be deposited and connected to an electrode having a single crystal tip 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 explanation of the drawing]

FIGS. 1A to 1F are schematic partial cross-sectional views for explaining the manufacturing process of an electron-emitting device according to a first embodiment of the manufacturing method of the present invention. FIG. 2(A) and FIG. 2(B) are illustrations of the selective deposition method. FIG. 3 is a graph showing changes over time in the nucleation density of the 5i02 deposition surface and the silicon nitride deposition surface. FIGS. 4(A) to 4(C) are formation process diagrams showing an example of a method for forming a single crystal. 5(A) and 5(B) are perspective views of the substrates in FIG. 4(A) and FIG. 4(C). FIGS. 6(A) to 6(C) are forming process diagrams showing other examples of the single crystal forming method. FIG. 7 is a graph showing the relationship between the flow rate ratio of SiH4 and NH3 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 cross-sectional view showing an example of a field effect type electron-emitting device. FIGS. 11(A) to 11(D) are schematic process diagrams for explaining the manufacturing method. ■・・・Base 2・・Φ・・Insulating layer 3・No.・Concavity 4.10-・06. Opening 5...Nucleation base 6.7...Single crystal 8...Electrode 9 with a pointed head...Fist/Pal 1 [Polar layer agent, patent attorney, Jo Yamashita Figures 1 to 2 Figure 2 (A) (E3) Figure 3 rL and Tomo (Threat) $4 Figure (A) CB) Figure 7 NH3/SiH4 L quantity ratio Figure 8 S1/N Child and Hezuki et al.

Claims (2)

[Claims] (1) A base body having a conductive material surface, an insulating layer provided on the base body having an opening, and a nucleation density sufficiently higher than that of the material of the insulating layer, and only a single nucleus formed in the insulating layer. an electrode provided on the insulating layer and having a tip of a crystal grown around a single nucleus grown in the dissimilar material; It has an extraction electrode provided near the head,
An electron-emitting device characterized in that the conductive material surface and an electrode having a pointed head are connected through the opening. (2) forming an insulating layer on a substrate having a conductive material surface; and forming an insulating layer on the insulating layer with a nucleation density sufficiently higher than that of the material of the insulating layer and sufficiently fine that only a single nucleus grows. forming a dissimilar material, forming an opening in the insulating layer to expose a part of the surface of the conductive material, and growing a crystal around a single nucleus grown in the dissimilar material. A method for manufacturing an electron-emitting device, comprising the steps of: forming an electrode having a pointed portion, and growing a crystal on a surface of a conductive material exposed in the opening, and connecting the electrode to the electrode having the pointed portion.