JPH05345696A - Production of diamond film - Google Patents

Abstract

PURPOSE:To obtain a diamond film applicable to high-temperature electronic devices, showing excellent characteristics such as hardness, corrosion resistance and heat resistance. CONSTITUTION:A carbon-containing target 7 is irradiated with irradiated with a first ionic beam 6 and sputtered. Carbon is fed to the surface of a substrate 11 opposing to the target 7 and a dopant element-containing second ionic beam 9 is injected to the surface of the substrate 11.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a diamond film, and in particular, it exhibits excellent properties such as hardness, corrosion resistance, and heat resistance, and is a novel material for application to high temperature electronic equipment. Regarding improvement.

[0002]

2. Description of the Related Art Generally, diamond is hard and has excellent heat resistance, has a large thermal conductivity, has an extremely large band gap, and has a mobility as high as that of Si electrons for both electrons and holes. In addition, due to its low specific induction, it has attracted attention as a high-temperature semiconductor and is being actively researched and developed.
Among them, the following two are well considered. The first conventional example is examined by the group of VaviLov et al. Of the Soviet Union, as described in the diamond semiconductor disclosed on pages 10 to 15 of New Diamond magazine issued by Ohmsha in 1986. This is a method that utilizes the ion implantation method that is performed in the manufacture of existing semiconductor elements such as Si and GaAs. This is because B, Al, P, C, Li, Ar, etc. are used as a dopant element in diamond, and 10 ¹⁵ to 10 ¹⁶ ions are applied at an energy of 40 to 100 KeV.
/ Cm ² of ion implantation and annealing at 1400 ° C. for 2 hours to obtain semiconductor diamond. Next, the second conventional example is a method of utilizing the diamond vapor phase synthesis method. That is, as described in the method for producing an n-type semiconductor diamond film disclosed in JP-A-62-70295, the dopant element P, As or Sb is formed by the microwave plasma CVD method or the thermal decomposition CVD method. A semiconductor diamond film is obtained by thermally decomposing or plasma-decomposing a reaction gas composed of a gas containing hydrogen, a hydrocarbon gas and hydrogen.

[0003]

The conventional diamond film manufacturing method has the following problems because it is configured as described above. That is, in the above-described ion implantation method, the ion implantation depth is very shallow (submicron) and the crystal itself is damaged by the ion implantation, so that sufficient semiconductor characteristics cannot be obtained. In particular, n-type semiconductor diamond is disclosed in, for example, Japanese Patent Application Laid-Open No. 62-70295, but it is said that it has not been obtained so far. Further, in order to recover damage, heat treatment at a high temperature of 1000 ° C. or higher is required, which is difficult to handle, costly, and the product value is not stable. In addition, in the above-mentioned method for producing an n-type semiconductor diamond film by diamond vapor phase synthesis, plasma CVD method or thermal decomposition C
Since it is a VD method, high temperature treatment (700-800 ° C or higher)
Therefore, there are problems that it is difficult to handle, large stress remains in the film, it is easily broken during use, and it is extremely difficult to control the amount of impurity elements (dopants).

The present invention has been made in order to solve the above problems. In particular, a dopant ion beam is injected at the same time as low temperature film formation by sputtering with an ion beam to obtain hardness, corrosion resistance and heat resistance. It is an object of the present invention to provide a method for producing a diamond film, which exhibits excellent characteristics as described above and is applicable to high-temperature electronic devices.

[0005]

The method for producing a diamond film according to the present invention is a method for producing a diamond film in which sputtered particles and implanted ions are mixed on the surface of a substrate to form a mixing film. Is a method of irradiating a target including a target and sputtering, supplying carbon to the surface of the substrate provided facing the target, and injecting an ion beam containing a dopant element while aggregating the carbon on the surface of the substrate. ..

More specifically, a gas containing a dopant element and an inert gas are introduced into one ion source, and a composite ion beam of an ion beam containing the dopant element and an inert gas ion beam is generated. The ion beam is separated into a first ion beam and a second ion beam, which are independent of each other on the trajectory of the mass spectrometer, and the target is irradiated with the first ion beam composed of the inert gas ion beam, and sputtering is performed to perform sputtering of the substrate. It is a method of supplying carbon to the surface and injecting the second ion beam containing the other dopant element while aggregating the carbon on the surface of the substrate.

More specifically, a gas containing a dopant element, a hydrocarbon gas and an inert gas are introduced into one ion source, and an ion beam containing the dopant element, a hydrocarbon gas ion beam and an inert gas ion beam are introduced. A composite ion beam is generated, and the composite ion beam is separated into a first ion beam and a second ion beam, which are independent of each other, on the trajectory of the mass spectrometer, and is inert to the hydrocarbon gas ion beam or the hydrocarbon gas ion beam. While irradiating the target with the first ion beam composed of a complex ion beam with a gas ion beam to form a carbon atom layer containing hydrogen on the substrate by sputtering, the first ion beam containing the dopant element is formed. This is a method of implanting two ion beams.

More specifically, a gas containing a dopant element, a carbon oxide gas and an inert gas are introduced into one ion source, and an ion beam containing the dopant element, a carbon oxide gas ion beam and an inert gas ion beam are introduced. A composite ion beam is generated, and the composite ion beam is separated into a first ion beam and a second ion beam, respectively, on the orbit of the mass spectrometer, and the carbon dioxide ion beam or the carbon dioxide ion beam and an inert gas ion are separated. The second ion containing the dopant element while irradiating the target with a first ion beam composed of a complex ion beam with the beam to form an atomic layer of carbon containing oxygen on the substrate by sputtering. This is a method of injecting a beam.

More specifically, it is a method in which the ion beam containing the dopant element implanted into the substrate is larger than the incident angle at which the maximum sputtering yield is obtained and the sputtering rate is smaller than 1.0.

More specifically, it is a method in which the dopant element is one or more selected from the group consisting of B, Al, P, As, Li and Sb.

More specifically, it is a method of blowing hydrogen gas onto the target and the substrate.

[0012]

In the method for producing a diamond film according to the present invention, a target containing carbon is irradiated with the first ion beam for sputtering, and carbon is supplied to the surface of the substrate provided facing the target. Second, containing a dopant element while aggregating carbon on the surface of the substrate
By injecting the ion beam, a semiconductor diamond film of an arbitrary film layer having stable quality at room temperature can be obtained at low cost.

[0013]

The preferred embodiments of the method for producing a diamond film according to the present invention will be described in detail below with reference to the drawings.
1 and 2 show an apparatus applied to the method for producing a diamond film according to the present invention. FIG. 1 is a schematic configuration diagram and FIG. 2 is a detailed configuration diagram of the mixing chamber of FIG. In FIG. 1, reference numeral 1 denotes an ion source, and the ion source 1 has first and second gas introduction pipes 1a, 1a for introducing two kinds of ion source gases (for example, Ar and PH ₃ ).
b is provided. Outside the ion emission port 1C formed in the ion source 1, the emitted ions (Ar ⁺ ,
Accelerating electrode 2 for accelerating P ⁺ ) into a composite ion beam 3
Is provided.

On the output side 2a of the accelerating electrode 2, a mass spectrometer 4 is provided on the trajectory of the composite ion beam 3, and the composite ion beam 3 is independently isolated by the applied magnetic field. The two ion beams 6 and 9 are separated. At the output end 4a of the mass analyzer 4, a first deflecting unit 5a capable of individually finely adjusting the loci of the independent first and second ion beams 6 and 9 separated by the mass analyzer 4 by an electric field, and A composite ion beam deflector 5 composed of the second deflection separation 5b is provided.

Of the ion beams 6 and 9 that have passed through the composite ion beam deflector 5, one of the ion beams 6 and 9 having a large mass A
The r ⁺ first ion beam 6 goes straight as it is and irradiates the target 7 in the mixing chamber 12 to generate sputtering atoms 8. On the other hand, the P ⁺ second ion beam 9 containing the dopant element having a small mass is the beam. Scanner 1
Substrate 11 in the mixing camber 12 passing through 0
Irradiate. The above-mentioned mass spectrometer 4 uses each ion beam 6,
The ion beams 6 and 9 having a magnetic field applied in the direction perpendicular to the locus of 9 and passing through the magnetic fields have the same accelerated voltage, but the atomic weight (mass number) peculiar to the atom.
And draw a curved locus with a radius of curvature ρ corresponding to the ratio of the number of charged ions. For example, in the case of Ar ⁺ (ρ ₁ ) and P ⁺ (ρ ₂ ), Equation (1) in the following equation 1

[0016]

[Equation 1]

The trajectories of the first ion beam and the second ion beam are separated. In addition, the target 7
The mixing film 11 a is formed on the substrate 11 by the sputtering atoms 8 generated by the irradiation of the first ion beam 6. Further, the mixing chamber 12 in which the target 7 and the substrate 11 are installed is provided with a reaction gas introducing pipe 15 for introducing a reaction gas 14 which reacts with the sputtering atoms 8 and the mixing thin film 11a. The trajectories of the ion beams 6 and 9 from the ion source 1 to the target 7 and the substrate 11 described above are housed in a container (not shown) and maintained in a vacuum of 10 ⁻⁴ to 10 ⁻⁸ Torr. Next, an example of an experiment actually performed by the applicant based on the above-mentioned configuration will be described.

[0018]

[Experimental Example 1] Ar gas 0.1 ccM and PH ₃ gas 0.06 ccM were introduced into the ion source 1 from the respective gas introduction pipes 1a and 1b to generate a composite ion beam 3 of Ar ⁺ and P ⁺ . A voltage of 20 KV is applied to the accelerating electrode 2 of the composite ion beam 3 to extract it from the ion emission port 1C of the ion source 1, and a current 13A is applied to the electromagnet of the mass analyzer 4 to generate a magnetic field to generate Ar ⁺ and P ⁺ . Separated into Ar ⁺ (ion beam current 30
0 μA) is applied to a target 7 made of graphite (purity 99.995%) with an irradiation angle θ ₁ = 75 ° and sputtered, and P ⁺ (ion beam current 30 μA) is irradiated with silicon with an irradiation angle θ ₂ = 80 °. The substrate 11 was irradiated. After irradiation for 8 hours, film thickness 200μm, film resistance 400Ω · c
A diamond-like carbon film containing m P was obtained.

[0019]

[Experimental Example 2] Ar gas of 0.1 ccM and PH ₃ gas of 0.06 ccM were introduced into the ion source 1 from the respective gas introduction tubes 1a and 1b to generate a composite ion beam 3 of Ar ⁺ and P ⁺ . A voltage of 20 KV is applied to the accelerating electrode 2 of the composite ion beam 3 to extract it from the ion emission port 1C of the ion source 1, and a current 13A is applied to the electromagnet of the mass analyzer 4 to generate a magnetic field to generate Ar ⁺ and P ⁺ . Separated into Ar ⁺ (ion beam current 30
0 μA) is applied to a target 7 made of graphite (purity 99.995%) with an irradiation angle θ ₁ = 75 ° and sputtered, and P ⁺ (ion beam current 30 μA) is irradiated with silicon with an irradiation angle θ ₂ = 80 °. The substrate 11 was irradiated. At that time, the reaction gas 14 consisting of H ₂ gas was passed through the reaction gas introduction pipe 15 into the mixing chamber 12 to obtain 0.04 cc.
M was introduced. After irradiation for 8 hours, film thickness 200μm, film resistance 1
A diamond-like carbon film containing P of KΩ · cm was obtained.

[0020]

[Experimental Example 3] N ₂ gas of 0.1 ccM and B ₂ H ₆ gas and CO gas of 0.06 ccM were introduced into the ion source 1 from the gas introduction pipes 1a and 1b, respectively, and N ₂ ⁺ , B ⁺ , and CO ⁺ of A composite ion beam 3 was generated. The composite ion beam 3 is applied to the accelerating electrode 2 with a voltage of 20 KV, extracted from the ion emission port 1C, and a current 13A is applied to the electromagnet of the mass analyzer 4 to generate a magnetic field to generate N ₂ ⁺ , B ⁺ and CO ^+. And separated into N ₂ ⁺ and CO ⁺ (ion beam current 100 μA) irradiation angle θ ₁ =
The graphite 7 (purity 99.995%) at 75 ° is irradiated and sputtered, and B ⁺ (ion beam current 30 μA) is applied to the beam scanner 10 at 500 Hz,
Irradiation angle θ ₂ = 80 while vibrating by applying a voltage of 1 KV
The silicon substrate 11 having a temperature of 90 ° was irradiated. At that time, 0.04 ccM of H ₂ gas was introduced into the mixing chamber 12 through the reaction gas introducing pipe 15. After irradiation for 8 hours, film thickness 250
A diamond-like carbon film containing B having a thickness of μm and a film resistance of 1 Ω · cm was obtained.

[0021]

[Experimental Example 4] CH ₄ gas of 0.1 ccM and N ₂ gas and PH ₃ gas of 0.06 ccM were introduced into the ion source 1 from the respective gas introduction pipes 1a and 1b to form a composite of CH ₃ ⁺ , P ⁺ and N ⁺ . Ion beam 3 was generated. This composite ion beam 3 is loaded on the accelerating electrode 2 with a voltage of 20 KV, extracted from the ion emission port 1C, and a current of 11 A is applied to the electromagnet of the mass spectrometer 4 to generate a magnetic field to generate N ⁺ , CH ₃ ⁺ and P ^+. Separated into and N ⁺ and C
Irradiation angle θ ₂ = 7 with H ₃ ⁺ (ion beam current 200 μA)
The graphite (purity 99.995%) target 7 was placed on the substrate 11 of FIG. 1 at 5 ° and was irradiated and sputtered, and P ⁺ (ion beam current 20 μA) was irradiated at an irradiation angle θ ₁ = 80 °. The silicon substrate 11 placed at the position of the target 7 was irradiated. After irradiation for 8 hours, film thickness 20
An n-type semiconductor diamond film containing P having a thickness of 0 μm and a film resistance of 100 Ω · cm was obtained. That is, although not shown in FIG. 1, this experimental example describes a case where the positions of the target 7 and the substrate 11 are opposite to each other.

As shown in FIG. 3, the ion beam 6 containing the impurity dopant element to be implanted into the substrate 11 is larger than the incident angle at which the maximum sputtering yield is obtained and the sputtering rate is smaller than 1.0. The range A is used. It is preferable to use at least one selected from the group consisting of B, Al, P, As, Li, and Sb as the dopant element, and to form a film while blowing hydrogen gas on the target 7 and the substrate 11. It goes without saying that you can also do. Further, a gas containing a dopant element, a hydrocarbon gas and an inert gas are introduced into the ion source 1 to generate a composite ion beam 3 of an ion beam containing the dopant element, a hydrocarbon gas ion beam and an inert gas ion beam. The target 7 is irradiated with the first ion beam 6 composed of a hydrocarbon gas ion beam or a composite ion beam of a hydrocarbon gas ion beam and an inert gas ion beam, and a carbon atomic layer containing hydrogen is formed on the substrate 11. It is also possible to inject the second ion beam 9 while forming a film. Further, a gas containing a dopant element, a carbon oxide gas and an inert gas are introduced into the ion source 1 to generate a composite ion beam 3 of an ion beam containing the dopant element, a carbon oxide gas ion beam and an inert gas ion beam. The target 7 is irradiated with a first ion beam 6 composed of a carbon oxide ion beam or a composite ion beam of a carbon oxide ion beam and an inert gas ion beam,
It is also possible to implant the second ion beam 9 while forming a carbon atom layer containing oxygen on the substrate 11.

[0023]

Since the method for producing diamond according to the present invention is configured as described above, the following effects can be obtained. That is, 2 from one ion source
Generate more than one type of ion beam and separate them into their respective orbits by the mass spectrometer.
The second ion beam of the other dopant element while irradiating the target of graphite with the ion beam to perform sputtering, supplying the sputtered atoms of carbon to the surface of the substrate and causing the carbon to aggregate on the surface of the substrate to generate diamond. By injecting, the semiconductor diamond film having an arbitrary film thickness with stable quality can be stably obtained at low cost by controlling the dopant injection amount at room temperature. Therefore, the effect of inexpensively supplying the base material of an electronic device applied to high-temperature electronic equipment is extremely important.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an apparatus applied to a diamond manufacturing method according to the present invention.

2 is an enlarged detailed configuration diagram showing the mixing chamber of FIG. 1. FIG.

FIG. 3 is a characteristic diagram showing a relationship between an incident angle of an ion beam and a sputtering yield.

[Explanation of symbols]

 1 Ion Source 3 Composite Ion Beam 4 Mass Spectrometer 6 First Ion Beam 7 Target 9 Second Ion Beam 11 Substrate

Claims (7)

[Claims] 1. Sputtered particles and implanted ions on a substrate
(11) In the method for producing a diamond film, which is mixed on the surface to form a mixing film (11a), a target (7) containing carbon is irradiated with a first ion beam (6) and is sputtered, Supplying carbon to the surface of the substrate (11) provided so as to face (7), and injecting a second ion beam (9) containing a dopant element on the surface of the substrate (11) while aggregating carbon. And a method for manufacturing a diamond film. 2. A gas containing a dopant element and an inert gas are introduced into one ion source (1) to generate a composite ion beam (3) of an ion beam containing the dopant element and an inert gas ion beam. , This composite ion beam
(3) is separated into a single first and second ion beam (6, 9) on the orbit of the mass spectrometer (4), and the first ion beam (6) composed of the inert gas ion beam is separated. The target (7) is irradiated and sputtered to the substrate (11)
2. The diamond film according to claim 1, wherein carbon is supplied to the surface of the substrate, and the second ion beam (9) containing the other dopant element is injected while aggregating the carbon on the surface of the substrate (11). Manufacturing method. 3. A gas containing a dopant element, a hydrocarbon gas and an inert gas are introduced into one ion source (1), and an ion beam containing the dopant element, a hydrocarbon gas ion beam and an inert gas ion beam are provided. The composite ion beam (3) is generated, and the composite ion beam (3) is separated into the first and second ion beams (6, 9) respectively on the orbit of the mass spectrometer (4), and the carbonization is performed. The target (7) is irradiated with the first ion beam (6) composed of a hydrogen gas ion beam or a composite ion beam of the hydrocarbon gas ion beam and an inert gas ion beam, and the substrate is sputtered ( 11. The method for producing a diamond film according to claim 1, wherein the second ion beam (9) containing the dopant element is implanted while forming a carbon atom layer containing hydrogen on the layer 11). 4. A gas containing a dopant element, a carbon oxide gas and an inert gas are introduced into one ion source (1), and an ion beam containing the dopant element, a carbon oxide gas ion beam and an inert gas ion beam are provided. The composite ion beam (3) is generated, and the composite ion beam (3) is separated into the first and second ion beams (6, 9) respectively on the orbit of the mass spectrometer (4), and the oxidation is performed. On the substrate (11), the target (7) is irradiated with a first ion beam (6) composed of a carbon ion beam or a complex ion beam of the carbon dioxide ion beam and an inert gas ion beam, and the target is sputtered. The method for producing a diamond film according to claim 1, wherein the second ion beam (9) containing the dopant element is implanted while forming a carbon atom layer containing oxygen in the film. 5. The second ion beam containing the dopant element to be implanted into the substrate (11) is larger than an incident angle at which the maximum sputtering yield is obtained and the sputtering rate is smaller than 1.0. The method for producing a diamond film according to claim 1. 6. The dopant element is B, Al, P, A
The method for producing a diamond film according to claim 1, wherein the diamond film is one or more selected from the group consisting of s, Li and Sb. 7. The method for producing a diamond film according to claim 1, wherein hydrogen gas is blown onto the target (7) and the substrate (11).