Boron-containing diamond film forming method and manufacturing device

Abstract

The present invention provides a method for forming a boron-containing diamond film (MPCVD method) that does not use a boron-containing gas G1 as a boron doping element source. [Solution] A method for producing boron-containing diamond films using the MPCVD method, in which a film-forming gas G0 is supplied from a film-forming gas inlet S0, an exhaust gas G2 is discharged from an exhaust port E, and boron-containing diamond is deposited on a substrate P0, characterized in that the film-forming gas G0 is supplied from a film-forming gas inlet S0 and a boron-containing quartz part 95 constituting a quartz injection head 90 is used as a boron doping element source.

Description

[Technical Field]

[0001] The present invention relates to a method and apparatus for forming a boron-containing diamond film. [Background technology]

[0002] Currently, high-quality boron-containing CVD diamond films are typically produced using the MPCVD method with dish-shaped and cylindrical chambers (see Figures 1 and 11(A) for dish-shaped and cylindrical chambers). These conventional methods require the introduction of a boron-containing gas G1 into the reaction chamber of the MPCVD equipment via a separate vent pipe, and the boron-containing CVD diamond film can be formed by reacting it with other gases under set conditions such as power and air pressure. Boron-containing diamond deposition requires a boron-doping element source, and the current method of obtaining a boron-doping element source is mainly to introduce boron-containing gas G1 into the MPCVD equipment reaction chamber through a vent pipe (Figure 1). The drawbacks of the prior art are as follows: (1) The first drawback of the prior art is that the boron-containing gas G1 is highly toxic and extremely harmful to human health, and at the same time, is flammable and explosive, posing a potentially serious safety problem. In the present invention, as an alternative to the method of introducing boron-containing gas G1 into the MPCVD equipment reaction chamber through a vent pipe as a method of obtaining a boron doping element source, a boron-containing quartz part 95 is placed on the deposition stage P01 at the center of the chamber, and the top of the boron-containing quartz part is adjacent to the top of the chamber, so that the boron doping element is uniformly released, thereby solving the first problem of the present invention (Figure 2). The boron-containing gas G1 contains borane and is toxic, but the boron-containing quartz part 95 is a solid material, and the borons released from the solid material are not toxic or have very little toxicity. (2) The second drawback of the prior art is that when the boron-containing gas G1 is introduced into the chamber through the vent pipe, the distribution of the boron-containing gas G1 becomes uneven, which affects the quality of the boron-containing diamond film deposition. In order to overcome the second drawback of the conventional technology, the present inventors have come up with the following two solutions (characteristic constituent features). (2-1) The first characteristic element In the present invention, a boron intake method (means) using a boron-containing quartz part 95 (solid material) is used as an alternative method (means) to the boron gas inhalation method (means), which is the conventional source of boron doping elements. This has the remarkable effect of releasing the boron doping elements more uniformly than the boron gas inhalation method (means). This is because the distribution of boron in the boron-containing quartz part 95 is very uniform, and the boron-containing quartz part can release boron uniformly (this solves the second problem of the present invention described below). (2-2) The second characteristic element In addition to the first characteristic feature, the present invention can achieve the remarkable effect of the second characteristic feature as follows. The quartz injection head 90 consisting of the boron-containing quartz part 95 employs a method for uniformly releasing boron doping elements by using a large number of holes and their regular arrangement (for example, the boron-containing diamond film manufacturing method described in any one of claims 4 to 6, and the boron-containing diamond film manufacturing apparatus 100 described in any one of claims 10 to 12), thereby solving the second problem of the present invention described below. DISCLOSURE OF THE INVENTION

[0003] The inventors have completed the present invention as a result of extensive research in light of the drawbacks of the prior art. [Prior art documents] [Patent documents]

[0004] When we conducted an FI and keyword search for the boron-containing diamond film manufacturing method (manufacturing apparatus) related to the present invention, we were unable to find any documents describing inventions similar to the present invention (the invention described in any of claims 1 to 12), so we will omit the description of the patent documents. Summary of the Invention [Problem to be solved by the invention]

[0005] First problem to be solved by this invention The first problem to be solved by the present invention is: The present invention provides a method (manufacturing means) for forming a boron-containing diamond film by utilizing the MPCVD method, without using a boron-containing gas G1 as a boron doping element source. Second problem to be solved by this invention The second problem to be solved by the present invention is: The present invention provides a method (manufacturing means) for producing a boron-containing diamond film, which overcomes the drawback of the prior art that when a boron-containing gas G1 is introduced into a chamber through a vent pipe, the distribution of the boron-containing gas G1 becomes uneven, affecting the quality of the boron-containing diamond film. [Means for solving the problem]

[0006] The means for solving the problem are the inventions described in each claim of the [Claims] of this application. In order to resolve any doubts regarding the interpretation of terms in the claims, specification, drawings, etc., the following explanations of terms are provided. <Terminology> ******************************************************* <About the (right-handed) XYZ coordinate system> In the present invention, the coordinate system is a right-handed XYZ coordinate system. In principle, the XYZ coordinate system is defined as follows (Figure 9). The X direction refers to the direction from the front to the back (horizontal direction). The Y direction refers to the vertical direction (anti-gravity direction). The Z direction refers to the direction from the left side to the right side (horizontal direction) towards X. With the center of gravity of the object (for example, a boron-containing diamond film-forming apparatus) as the center, the side closer to the center is defined as the inner side, and the side farther from the center is defined as the outer side. ******************************************************* <Relationship between the XYZ coordinate system and the six views (front view, rear view, plan view, bottom view, left side view, right side view)> The relationship between the XYZ coordinate system and the six views will be described below. Already, in <(right-handed) XYZ coordinate system>, the definition of the (right-handed) XYZ coordinate system has been given (Figure 9). In such an XYZ coordinate system, the six views (front view, rear view, plan view, bottom view, left side view, right side view) are defined as follows (Figure 9) Among the six views, first, the front view is defined. In the object, the view that an observer on the front side can see when observing the object on the rear side is defined as the front view (from the front side of the paper to the back side of the paper is the X direction). Then, the rear view is defined. The view that an observer on the rear side can see when observing the object on the front side is defined as the rear view (from the front side of the paper to the back side of the paper is the -X direction). Next, the plan view is defined. The view that an observer on the upper side can see when observing the object on the lower side is defined as the plan view (from the front side of the paper to the back side of the paper is the -Y direction). Then, the bottom view is defined. The view that an observer on the lower side can see when observing the object on the upper side is defined as the bottom view (from the front side of the paper to the back side of the paper is the Y direction). Next, the left side view is defined. The view that an observer on the left side can see when observing the object on the right side is defined as the left side view (from the front side of the paper to the back side of the paper is the Z direction). Then, the right side view is defined. The view that an observer on the right side can see when observing the object on the left side is defined as the right side view (from the front side of the paper to the back side of the paper is the -Z direction). Here, A front perspective view is a view in which an observer at the front side observes an object at the rear side from the upper right. Furthermore, once the six views (front view, back view, top view, bottom view, left side view, and right side view) are identified, the XYZ coordinate system defined above is uniquely identified for each identified view. ******************************************************* ●Boron-containing diamond (also called boron-doped diamond) BD refers to diamond in which some of the carbon atoms that make up the diamond have been replaced with boron atoms. Doping diamond with boron affects its electrical conductivity. If the doping concentration is low, the diamond is an insulator, but depending on the doping concentration, it changes from a semiconductor to a conductor. It has been reported that at high doping rates of around 3%, diamond exhibits superconducting properties at extremely low temperatures. The boron-containing diamond film forming manufacturing method (manufacturing apparatus 100) refers to an MPCVD method (manufacturing apparatus 99) that uses the MPCVD method to form a thin film of boron-containing diamond (boron-doped diamond) BD (form a film of boron-containing diamond BD). ●MPCVD (Microwave Plasma CVD) is a method in which energetic electrons generated by microwave discharge separate gas molecules into ions and electrons (in a plasma state), and diamond is synthesized on a specified substrate. The MPCVD apparatus 99 is an apparatus (prior art) for depositing a boron-containing diamond BD on a substrate P0 using the MPCVD method (microwave plasma CVD method). ●Film formation refers to forming a thin film on the surface of an object. The deposition gas G0 in this invention uses hydrogen as the carrier gas and methane as the working gas, with methane being 6-12% of hydrogen. Nitrogen, oxygen, or borane can also be added at ppm rates. The deposition gas intake port S0 is the intake port for taking in the deposition gas G0. ●Boron-containing gas G1 generally refers to various boranes (borane is a compound of boron and hydrogen, a general term for boron hydrides), such as BH3 and B2H6. Chamber CB refers to the space inside the device of the present invention. In the present invention, the chamber consists of two chambers. Specifically, chamber CB is composed of a lower dish-shaped chamber CB2 and an upper cylindrical chamber CB1 (Figures 1, 2, and 11(A)). In the present invention, boron doping refers to replacing (doping) some of the carbon atoms that make up diamond with boron atoms. ●A boron doping element source is a source that emits boron to replace some of the carbon atoms that make up diamond with boron atoms. In the present invention, the boron doping element source refers to a quartz part that uniformly contains boron for replacing some of the carbon atoms that make up the diamond with boron atoms. In the prior art, the boron doping element source refers to a boron-containing gas G1 that contains boron for replacing some of the carbon atoms that constitute diamond with boron atoms. In the present invention, this refers to a quartz part containing boron in order to replace some of the carbon atoms constituting diamond with boron atoms. The substrate P0 refers to a plate on which the boron-containing diamond thin film is formed. The deposition stage P01 is a stage on which the substrate P0 is placed. The quartz injection head 90 is an airflow injection head (shower head) made up of a boron-containing quartz part 95 (solid material) that ejects a boron-containing gas G1. The boron-containing quartz parts 95 are solid parts made of boron and quartz that uniformly release boron, and there are two types as follows: (first type) The first type is the traditional boron-doped silica glass (solid), ie, borax glass (borosilicate glass). Borax glass (borosilicate glass) is glass that is melted by mixing more than 5% boric acid, increasing its softening temperature and hardness. It is a typical example of heat-resistant glass and hard glass. It has a low coefficient of thermal expansion, making it more resistant to thermal shock than regular glass. Due to its excellent heat and chemical resistance, it is used in laboratory equipment and kitchenware. (Second type) The second type involves plating the surface of the quartz component with solid boron in a plating-like manner. Plating methods include chemical formation of thin boron films, such as PECVD (Plasma Enhanced Chemical Vapor Deposition), MOCVD (Metal Organic Chemical Vapor Deposition), PVD (Physical Vapor Deposition, a surface treatment method also known as physical vapor deposition), and electrical plating. ●Exhaust gas G2 refers to the exhaust gas that is no longer needed for synthesizing boron-containing diamond BD. The exhaust port E is an outlet for discharging the exhaust gas G2 that is no longer needed for synthesizing the boron-containing diamond BD out of the chamber CB. The gap 10 refers to the empty planar space between the top of the quartz injection head 90 and the top of the chamber CB. *The hole refers to a large number of holes regularly arranged in the quartz ejection head 90 (or one hole among a large number of holes) (FIGS. 4 to 8, 10). *Diameter d (cm) refers to the diameter (cm) of the hole in the quartz injection head 90 (FIGS. 7 to 8, 10, and 1). The aperture position r (cm) refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm) (FIGS. 7 to 8, 10). ● const. means a constant (cm 2 , cm). ●C1 is a constant (cm 2 ) ●Angle of incidence θ: The angle (°) that the jet makes with respect to the vertical direction (Y direction) (Figures 8 and 10). ●C2 is a constant (cm). <Differences between the prior art and the present invention (outline)> 1. The common features between the prior art and the present invention are as follows: Regarding the commonalities between the prior art and the present invention, first, both technologies are MPCVD methods for depositing high-quality boron-containing CVD diamond films. Second, the quality and uses of the boron-containing diamond BD deposited by the two technologies are basically the same. Third, except for the method of introducing boron, the methods of introducing the other raw material gases are the same. 2. Differences between the prior art and the present invention The differences between the prior art and the present invention are as follows: First, the boron doping element source was changed from boron-containing gas G1 to boron-containing quartz components. Second, the boron-containing gas vent pipes that had been installed in the existing dish-shaped and cylindrical chamber structures were removed, and boron-containing quartz components were added to the chambers. The first major difference is that the boron doping element source has been changed from boron gas to a boron-containing quartz part, and the second major difference is that a boron-containing quartz part has been added to the chamber. 3. Action of the present invention The present invention utilizes a novel method to place a boron source in a boron-containing quartz component within the chamber of the manufacturing facility, thereby eliminating the use of toxic and harmful gases during production. As shown in Figure 1, in MPCVD, a quartz injection head is placed on the deposition stage P01 in the center of the chamber. The top of the injection head is adjacent to the top of the chamber, with a gap of less than 1 mm. The lower support is in a designated position on the deposition stage. The structure of a typical boron-containing quartz injection head is shown in Figure 2. There are several possible designs for the injection head's holes. One is to increase the hole diameter in proportion to the radius of the injection head, so that the gas flow rate remains essentially constant relative to the head radius. Another is to change the direction of the holes from straight to radial, thereby achieving stable gas flow distribution. The boron content of the quartz injection head can be adjusted depending on the amount of boron doping in the diamond, making it possible to form a variety of boron-doped diamond films. 4. Effects of the present invention By adding boron-containing quartz components to the existing dish-shaped and cylindrical chamber structures, it can be used as a boron doping element source in the MPCVD diamond deposition process, and then boron-containing diamond deposition can be achieved. This method avoids the use of conventional boron-containing toxic gases, and the quartz components enable an orderly reaction with the gas diffusion, thereby achieving uniform boron-containing diamond deposition and effectively improving the quality of diamond deposition. <Calculation method for airflow (plasma flow) (part 1)> The "numerous regularly arranged holes" of the quartz ejection head 90 were calculated as follows to clarify the regularity (see FIGS. 4 to 7). n: Number of holes (number of holes in a circumference of radius r, 2πr (cm)) r: Radius from the center O of the holes to the hole position (cm) d: diameter of hole (cm) S: Range of fluid ejected from the hole (cm) ∝; symbol meaning proportional const.;Const.(cm 2 ,cm) C1;Constant(cm 2 ) C2.: Constant (cm) Here, the cross-sectional area of ​​the hole (cm 2 )=(π / 4)d 2 , Circumference length (cm) of radius r = 2πr Total area of ​​the hole circumference (cm 2 )=(π / 4)d 2 ×n Therefore, n∝2πr / d∝r / d ∴Total area of ​​the circumference of the hole (cm 2 )=(π / 4)d 2 ×n∝(π / 4)d 2 ×r / d =(π / 4)dr∝dr…Eq. (1-1) Also, from another perspective, Total area of ​​the hole circumference (cm 2 )=2πrS∝rS…(1-2) formula Equation (1-1) and equation (1-2) are solved simultaneously to obtain equation (1-3). dr∝rS (i.e., d∝S)…Eq. (1-3) (1) In equation (1-1), the total area (cm 2 )=const., then (A) is obtained. dr=const.=C1 That is, d==C1 / r…(A) On the other hand, in equation (1-2), the total area (cm 2 )=const., then We obtain equation (A'). rS=const.(S=const. / r)…(A') expression (2) In equation (1-3) (d∝S), if d=const., we obtain S=const. Here, d=const.…(B) formula S=const.…(B') expression therefore, Formula (A) represents the case of claims 4 and 10, Formula (B) represents the case of claims 5 and 11. <Calculation method for airflow (plasma flow) (part 2)> Regarding the "numerous regularly arranged holes" of the quartz ejection head 90, the following calculation was carried out to determine the regularity (see FIGS. 4 to 8 and 10). θ: Incident angle of jet (°) n: Number of holes r: Radius from the center O of the holes to the hole position (cm) d: Hole diameter (cm): diameter of the cross-sectional area of ​​the hole (cm) const.;Const.(cm 2 ) C2.: Constant (cm) Here, the cross-sectional area of ​​the hole (cm 2 )=(π / 4)d 2 , Circumference length (cm) of radius r = 2πr Total area of ​​the hole circumference (cm 2 )=(π / 4)d 2 ×n The fluid flow rate in the direction of gravity (-Y direction) is (π / 4)d 2 ×n×COS(θ) Also, n∝2πr / d∝r / d ∴Fluid flow rate in the gravity direction (-Y direction) = (π / 4)d 2 ×COS(θ)×n∝(π / 4)d 2 ×COS(θ)×r / d =(π / 4)dr×COS(θ)∝dr×COS(θ)= const.…(1-3) formula In equation (1-3), if r=const., d×COS(θ)=C2 ∴d=C2 / COS(θ) …(C) formula holds true. Formula (C) represents the case of claims 6 and 12. In Figures 8 and 10, the jet flow is jetted in a downward and rightward direction (within the YZ plane of the XYZ coordinate system) toward the paper, so no rotational force acts on the fluid and no swirling flow occurs. However, if the incident angle θ (°) of the jet flow has an angle θ' with respect to the YZ plane, a rotational force acts on the fluid and a swirling flow occurs. <Why are the regularly arranged numerous holes in the quartz injection head 90 a distinctive feature?> (1) When the regularly arranged numerous holes (characteristic constituent element) of the quartz injection head 90 are not introduced Since there are no distinctive features to control the airflow, the airflow can be likened to a pipe flow. Since there are no regularly arranged holes, the airflow remains non-swirling (remains swirling) and the airflow is relatively concentrated in the center, so the amount of gas flowing in is larger in the center and smaller in the wall area, resulting in an unbalanced flow. This follows from a fundamental property of fluids: the fluid in a pipe has the fastest flow velocity in the center of the pipe and zero velocity near the wall. Therefore, the gas flow velocity (or flow rate) on the same cross section of the pipe will be different, with a faster flow velocity (higher flow rate) in the center and a slower flow velocity (lower flow rate) near the wall. (2) Introduction of a large number of regularly arranged holes in the quartz injection head 90 In order to correct the unbalanced flow as described above, the inventor came up with the idea of ​​this invention to equalize the amount of gas inflow by changing the area of ​​the aperture (size and number of apertures) depending on the location of the unbalanced flow. In this case, when a showerhead (quartz injection head 90) is added to the cross section of the fluid, the gas flow rate at each location is directly related to the area and number of channels (holes). For the same hole size, reducing the number of holes in the center may impede gas flow in the center. Reducing the gas flow in the central region is said to shift the gas flow to the edges, promoting uniform flow. A similar effect can be achieved by keeping the number of holes the same and reducing the number of holes in the center. The above holes are generally vertical. If the direction of the holes is tilted to a certain extent and the tilt direction is aligned with the direction of the airflow (gas flow), the airflow can rotate, forming a tornado-like effect. A stable air flow can be maintained (see Figures 8 and 10). The means for solving the problems are the inventions described in the claims of the present application, and the specific means for solving the problems are as follows. First invention (invention described in claim 1) The first invention (the invention described in claim 1) for solving the above problem is: This is a method for manufacturing boron-containing diamond films using the MPCVD method, in which a film-forming gas G0 is supplied from a film-forming gas inlet S0, an exhaust gas G2 is discharged from an exhaust port E, and boron-containing diamond BD is formed on a substrate P0, characterized in that the film-forming gas G0 is supplied from a film-forming gas inlet S0 and a boron-containing quartz part 95 constituting a quartz injection head 90 is used as a boron doping element source. Second invention (invention described in claim 2) The second invention (the invention described in claim 2) for solving the above problem is: 2. The method for depositing a boron-containing diamond film according to claim 1, wherein the deposition gas G0 is a mixed gas of methane gas and hydrogen gas. Third invention (invention described in claim 3) The third invention (the invention described in claim 3) for solving the above problem is: A method for producing a boron-containing diamond film as described in any one of claims 1 to 2, characterized in that a quartz injection head 90 consisting of a boron-containing quartz part 95 is placed on a film formation stage P01 at the center of a chamber CB, the top of the injection head 90 is adjacent to the top of the chamber CB, and the gap 10 is less than 1 mm. Fourth invention (invention described in claim 4) The fourth invention (the invention described in claim 4) for solving the above problem is: A method for forming a boron-containing diamond film according to any one of claims 1 to 3, characterized in that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (A). d=C1 / r……Equation (A) Here, the aperture position r refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). C1 is a constant (cm 2 ) Fifth invention (invention described in claim 5) A method for forming a boron-containing diamond film according to any one of claims 1 to 3, characterized in that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (B). d=const.……(B) formula Here, the aperture position r refers to the distance (cm) from the center of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). const. means a constant (cm). Sixth Invention (Invention described in claim 6) The sixth invention (the invention described in claim 6) for solving the above problem is: A method for forming a boron-containing diamond film according to any one of claims 1 to 3, characterized in that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (C). d=C2 / cos(θ)……(C) Here, the aperture position r (cm) refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). θ refers to the angle of incidence (°). C2 refers to a constant (cm). Seventh invention (invention described in claim 7) The seventh invention (the invention described in claim 7) for solving the above problem is: The boron-containing diamond film forming manufacturing apparatus 100 utilizes an MPCVD apparatus 99 that has a film forming gas inlet S0 for supplying a film forming gas G0, an exhaust port E for discharging an exhaust gas G2, and that forms a boron-containing diamond BD on a substrate P0, and is characterized in that it is equipped with a film forming gas inlet S0 for supplying a film forming gas G0, and a boron-containing quartz part 95 that constitutes a quartz injection head 90 as a boron doping element source. Eighth invention (invention described in claim 8) The eighth invention (the invention described in claim 8) for solving the above problem is: 8. The boron-containing diamond film manufacturing apparatus 100 according to claim 7, wherein the film-forming gas G0 is a mixed gas of methane gas and hydrogen gas. Ninth invention (invention described in claim 9) The ninth invention (the invention described in claim 9) for solving the above problem is: The boron-containing diamond film deposition manufacturing apparatus 100 described in claim 7 is characterized in that a quartz injection head 90 consisting of a boron-containing quartz part 95 is installed on a film deposition stage P01 at the center of the chamber CB, the top of the injection head 90 is adjacent to the top of the chamber CB, and the gap 10 is less than 1 mm. Tenth invention (invention described in claim 10) The tenth invention (the invention described in claim 10) for solving the above problem is: A boron-containing diamond film deposition manufacturing apparatus 100 as described in any one of claims 7 to 9, characterized in that the diameter d (cm) and diameter position r (cm) of the hole of the quartz injection head 90 satisfy formula (A). d=C1 / r……Equation (A) Here, the aperture position r refers to the distance (cm) from the center of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). C1 is a constant (cm 2 ) 11th invention (invention described in claim 11) The eleventh invention (the invention described in claim 11) for solving the above problem is: A boron-containing diamond film manufacturing apparatus 100 as described in any one of claims 7 to 9, characterized in that the diameter d (cm) and diameter position r (cm) of the hole of the quartz injection head 90 satisfy formula (B). d=const.……(B) formula Here, the aperture position r refers to the distance (cm) from the center of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). const. means a constant (cm). The twelfth invention (the invention described in claim 12) The twelfth invention (the invention described in claim 12) for solving the above problem is: A boron-containing diamond film manufacturing apparatus 100 as described in any one of claims 7 to 9, characterized in that the diameter d (cm) and diameter position r (cm) of the hole of the quartz injection head 90 satisfy formula (C). d=C2 / cos(θ)……(C) Here, the aperture position r (cm) refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). θ refers to the angle of incidence (°). const. means a constant (cm). [Effects of the Invention]

[0007] The method for forming and manufacturing a boron-containing diamond film according to the present invention is comprised of the characteristic constituent elements described above, and exhibits the following effects specific to the present invention in accordance with the characteristic constituent elements. Furthermore, according to the method for forming and manufacturing a boron-containing diamond film, which is configured with the above-mentioned characteristic constituent elements in accordance with each of the above-mentioned inventions, the problems of the present invention can be sufficiently solved. Effect of the first invention According to the first invention, In a method for manufacturing boron-containing diamond films using the MPCVD method, in which a film-forming gas G0 is supplied from a film-forming gas inlet S0, an exhaust gas G2 is discharged from an exhaust port E, and boron-containing diamond BD is formed on a substrate P0, the first and second problems that the present invention aims to solve can be achieved by the characteristic configuration requirements of supplying the film-forming gas G0 from a film-forming gas inlet S0 and using a boron-containing quartz part 95 that constitutes a quartz injection head 90 as a boron doping element source, and significant effects that could not be predicted by a person skilled in the art can be achieved. Effect of the second invention According to the second invention, Due to the characteristic constituent requirement that the film-forming gas G0 is a mixture of methane gas and hydrogen gas, the first and second problems that the present invention aims to solve can be achieved, and remarkable effects that could not be predicted by those skilled in the art can be achieved. Effect of the third invention According to the third invention, By installing a quartz injection head 90 consisting of a boron-containing quartz part 95 on a film formation stage P01 at the center of the chamber CB, with the top of the injection head 90 adjacent to the top of the chamber CB and a gap 10 of less than 1 mm, the first and second problems that the present invention aims to solve can be achieved, and significant effects that could not be predicted by a person skilled in the art can be achieved. Effect of the fourth invention According to the fourth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (A) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. Effect of the fifth invention According to the fifth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (B) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. Effect of the sixth invention According to the sixth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (C) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. Effect of the seventh invention According to the seventh invention, In a boron-containing diamond film formation manufacturing apparatus 100 utilizing an MPCVD apparatus 99 that has a film formation gas inlet S0 for supplying a film formation gas G0, an exhaust port E for discharging an exhaust gas G2, and that forms a boron-containing diamond BD on a substrate P0, the apparatus has the characteristic configuration requirements of having a film formation gas inlet S0 for supplying a film formation gas G0 and a boron-containing quartz part 95 that constitutes a quartz injection head 90 as a boron doping element source, which makes it possible to achieve the first and second problems that the present invention aims to solve, and to produce remarkable effects that would be unpredictable to those skilled in the art. Effect of the eighth invention According to the eighth invention, Due to the characteristic constituent requirement that the film-forming gas G0 is a mixture of methane gas and hydrogen gas, the first and second problems that the present invention aims to solve can be achieved, and remarkable effects that could not be predicted by those skilled in the art can be achieved. Effect of the ninth invention According to the ninth invention, By installing a quartz injection head 90 consisting of a boron-containing quartz part 95 on a film formation stage P01 at the center of the chamber CB, with the top of the injection head 90 adjacent to the top of the chamber CB and a gap 10 of less than 1 mm, the first and second problems that the present invention aims to solve can be achieved, and significant effects that could not be predicted by a person skilled in the art can be achieved. Effect of the 10th invention According to the tenth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (A) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. Effect of the eleventh invention According to the eleventh invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (B) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. Effect of the twelfth invention According to the twelfth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (C) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. BEST MODE FOR CARRYING OUT THE INVENTION

[0008] Hereinafter, the best mode for carrying out the method for forming a boron-containing diamond film according to the present invention will be described with reference to the drawings. [Fig. 1] Fig. 1 is a front view of the prior art. [Fig. 2] Fig. 2 is a front view of the present invention. [Fig. 3] Fig. 3 shows front views of boron-containing quartz parts 95. (A) shows a front view of a first type of boron-containing quartz part 95. (B) shows a front view of a second type of boron-containing quartz part 95. [Fig. 4] Fig. 4 shows a number of regularly arranged holes in a quartz injection head 90 that satisfies formula (A). Fig. 4(A) shows a plan view of the quartz injection head 90. Fig. 4(B) shows a cross-sectional view taken along the line AA. Fig. 4(C) shows a front view of the quartz injection head 90. Fig. 4(D) shows a perspective view of the quartz injection head 90. [Fig. 5] Fig. 5 shows a number of regularly arranged holes in a quartz injection head 90 that satisfies formula (B). Fig. 5(A) shows a plan view of the quartz injection head 90. Fig. 5(B) is a missing number. Fig. 5(C) shows a cross-sectional view taken along the arrow B-B. Fig. 5(D) shows a perspective view of the quartz injection head 90. [Fig. 6] Fig. 6 shows a number of regularly arranged holes in a quartz injection head 90 that satisfies formula (C). Fig. 6(A) shows a plan view of the quartz injection head 90. Fig. 6(B) is a missing number. Fig. 6(C) shows a cross-sectional view taken along the line B--B. Fig. 6(D) shows a perspective view of the quartz injection head 90. [Figure 7] Figure 7 is a reference diagram for the calculation method (part 1) of airflow (plasma flow). [Figure 8] Figure 8 is a reference diagram for the airflow (plasma flow) calculation method (part 2). Figure (A) shows a perspective view of the airflow (plasma flow) calculation method (part 2). Figure (B) shows a cross-sectional view of a fluid flowing into a hole in a boron-containing quartz part 95 at an incident angle θ (°). Figure (C) shows a view taken along the arrow AA in Figure (B), where the cross-sectional area of ​​the airflow = the cross-sectional area of ​​the hole = (π / 4)d 2 (cm) FIG. 9 is a diagram showing the relationship between the XYZ coordinate system and six views (front view, rear view, top view, bottom view, left side view, and right side view). 10(A) is a perspective view of a quartz injection head 90. FIG. 10(B) is a front cross-sectional view of a boron-containing quartz part 95. The upper diagram in FIG. 1(B) shows a front cross-sectional view of a boron-containing quartz part 95 that satisfies formula (A). The middle diagram in FIG. 9B shows a front cross-sectional view of a boron-containing quartz part 95 that satisfies the formula 95B. The lower diagram in FIG. 1(B) shows a front cross-sectional view of a boron-containing quartz part 95 that satisfies formula (C). [Fig. 11] Fig. 11(A) is a diagram showing the range of the chamber CB (the range indicated by the thick diagonal lines) in a front view of the invention. Fig. 11(B) is an enlarged view showing the area around the gap 10 and the quartz injection head 90 in the front view of the invention. The method for forming a boron-containing diamond film according to the present invention will be described below with reference to the drawings. 11111************************************************** In the method for producing a boron-containing diamond film of the present invention, In a method for producing boron-containing diamond films using the MPCVD method, a film-forming gas G0 is supplied from a film-forming gas inlet S0, an exhaust gas G2 is discharged from an exhaust port E, and a boron-containing diamond BD is formed on a substrate P0. The method is characterized in that a film-forming gas G0 is supplied from a film-forming gas inlet S0 and a boron-containing quartz part 95 constituting a quartz injection head 90 is used as a boron doping element source. Effect of the first invention According to the first invention, In a method for manufacturing boron-containing diamond films using the MPCVD method, in which a film-forming gas G0 is supplied from a film-forming gas inlet S0, an exhaust gas G2 is discharged from an exhaust port E, and boron-containing diamond BD is formed on a substrate P0, the first and second problems that the present invention aims to solve can be achieved by the characteristic configuration requirements of supplying the film-forming gas G0 from a film-forming gas inlet S0 and using a boron-containing quartz part 95 that constitutes a quartz injection head 90 as a boron doping element source, and significant effects that could not be predicted by a person skilled in the art can be achieved. 22222************************************************** In the above-mentioned method for producing a boron-containing diamond film, The method for forming a boron-containing diamond film is disclosed as described in claim 1, characterized in that the film forming gas G0 is a mixed gas of methane gas and hydrogen gas. Effect of the second invention According to the second invention, Due to the characteristic constituent requirement that the film-forming gas G0 is a mixture of methane gas and hydrogen gas, the first and second problems that the present invention aims to solve can be achieved, and remarkable effects that could not be predicted by those skilled in the art can be achieved. 33333************************************************** In the above-mentioned method for producing a boron-containing diamond film, A boron-containing diamond film deposition manufacturing method as described in any one of claims 1 to 2 is disclosed, characterized in that a quartz injection head 90 consisting of a boron-containing quartz part 95 is placed on a film deposition stage P01 in the center of a chamber CB, the top of the injection head 90 is adjacent to the top of the chamber CB, and the gap 10 is less than 1 mm. Effect of the third invention According to the third invention, By installing a quartz injection head 90 consisting of a boron-containing quartz part 95 on a film formation stage P01 at the center of the chamber CB, with the top of the injection head 90 adjacent to the top of the chamber CB and a gap 10 of less than 1 mm, the first and second problems that the present invention aims to solve can be achieved, and significant effects that could not be predicted by a person skilled in the art can be achieved. 44444************************************************** In the above-mentioned method for producing a boron-containing diamond film, A method for forming and manufacturing a boron-containing diamond film is disclosed, characterized in that the diameter d (cm) and diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (A). d=C1 / r……Equation (A) Here, the aperture position r refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). C1 is a constant (cm 2 ) Effect of the fourth invention According to the fourth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (A) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. 55555************************************************** In the above-mentioned method for producing a boron-containing diamond film, A method for forming and manufacturing a boron-containing diamond film is disclosed, characterized in that the diameter d (cm) and diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (B). d=const.……(B) formula Here, the aperture position r refers to the distance (cm) from the center of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). const. means a constant (cm). Effect of the fifth invention According to the fifth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (B) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. 66666************************************************** In the above-mentioned method for producing a boron-containing diamond film, A method for forming a boron-containing diamond film is disclosed, characterized in that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (C). d=C2 / cos(θ)……(C) Here, the aperture position r (cm) refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). θ refers to the angle of incidence (°). const. means a constant (cm). Effect of the sixth invention According to the sixth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (C) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. 77777************************************************** In the boron-containing diamond film forming manufacturing apparatus 100 of the present invention, The boron-containing diamond film forming manufacturing apparatus 100 utilizes an MPCVD apparatus 99 that has a film forming gas inlet S0 for supplying a film forming gas G0, an exhaust port E for discharging an exhaust gas G2, and that forms a boron-containing diamond BD on a substrate P0, and is characterized by having a film forming gas inlet S0 for supplying a film forming gas G0 and a boron-containing quartz part 95 that constitutes a quartz injection head 90 as a boron doping element source. Effect of the seventh invention According to the seventh invention, In a boron-containing diamond film formation manufacturing apparatus 100 utilizing an MPCVD apparatus 99 that has a film formation gas inlet S0 for supplying a film formation gas G0, an exhaust port E for discharging an exhaust gas G2, and that forms a boron-containing diamond BD on a substrate P0, the apparatus has the characteristic configuration of having a film formation gas inlet S0 for supplying a film formation gas G0 and a boron-containing quartz part 95 that constitutes a quartz injection head 90 as a boron doping element source, which makes it possible to achieve the first and second problems that the present invention aims to solve, and has been able to produce remarkable effects that would be unpredictable to those skilled in the art. 88888************************************************** In the above-mentioned method for producing a boron-containing diamond film, The boron-containing diamond film forming manufacturing apparatus 100 is disclosed as described in claim 7, characterized in that the film forming gas G0 is a mixed gas of methane gas and hydrogen gas. Effect of the eighth invention According to the eighth invention, Due to the characteristic constituent requirement that the film-forming gas G0 is a mixture of methane gas and hydrogen gas, the first and second problems that the present invention aims to solve can be achieved, and remarkable effects that could not be predicted by those skilled in the art can be achieved. 99999************************************************** In the above-mentioned method for producing a boron-containing diamond film, A boron-containing diamond film deposition manufacturing apparatus 100 is disclosed, characterized in that a quartz injection head 90 consisting of a boron-containing quartz part 95 is installed on a film deposition stage P01 in the center of a chamber CB, the top of the injection head 90 is adjacent to the top of the chamber CB, and the gap 10 is less than 1 mm. Effect of the ninth invention According to the ninth invention, By installing a quartz injection head 90 consisting of a boron-containing quartz part 95 on a film formation stage P01 at the center of the chamber CB, with the top of the injection head 90 adjacent to the top of the chamber CB and a gap 10 of less than 1 mm, the first and second problems that the present invention aims to solve can be achieved, and significant effects that could not be predicted by a person skilled in the art can be achieved. 101010************************************************ In the above-mentioned method for producing a boron-containing diamond film, A boron-containing diamond film forming manufacturing apparatus 100 is disclosed, characterized in that the diameter d (cm) and diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (A). d=C1 / r……Equation (A) Here, the aperture position r refers to the distance (cm) from the center of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). C1 is a constant (cm 2 ) Effect of the 10th invention According to the tenth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (A) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. 111111************************************************ In the above-mentioned method for producing a boron-containing diamond film, A boron-containing diamond film forming manufacturing apparatus 100 is disclosed, characterized in that the diameter d (cm) and diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (B). d=const.……(B) formula Here, the aperture position r refers to the distance (cm) from the center of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). const. means a constant (cm). Effect of the eleventh invention According to the eleventh invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (B) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. 121212************************************************ In the above-mentioned method for producing a boron-containing diamond film, A boron-containing diamond film forming manufacturing apparatus 100 is disclosed, characterized in that the diameter d (cm) and diameter position r (cm) of the hole in the quartz injection head 90 satisfy formula (C). d=C2 / cos(θ)……(C) Here, the aperture position r (cm) refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). θ refers to the angle of incidence (°). const. means a constant (cm). Effect of the twelfth invention According to the twelfth invention, The characteristic structural requirement that the diameter d (cm) and the diameter position r (cm) of the hole in the quartz injection head 90 satisfy the formula (C) makes it possible to achieve the first and second problems that the present invention aims to solve, and to achieve remarkable effects that would be unpredictable to a person skilled in the art. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 shows a front view of the prior art. [Figure 2] FIG. 2 shows a front view of the present invention. [Figure 3] 3A and 3B are front views of boron-containing quartz parts 95. (A) shows a front view of a first type of boron-containing quartz part 95. (B) shows a front view of a second type of boron-containing quartz part 95. [Figure 4] FIG. 4 shows a quartz injection head 90 with a large number of regularly arranged holes that satisfy formula (A). FIG. 4(A) shows a plan view of the quartz injection head 90. FIG. 4(B) shows a cross-sectional view taken along the line AA. FIG. 4(C) shows a front view of the quartz injection head 90. FIG. 4(D) shows a perspective view of the quartz injection head 90. [Figure 5] FIG. 5 shows a quartz injection head 90 with a large number of regularly arranged holes that satisfy formula (B). FIG. 5(A) shows a plan view of the quartz injection head 90. FIG. 5(B) is a missing number. FIG. 5(C) shows a cross-sectional view taken along the line B--B. FIG. 5(D) shows a perspective view of the quartz injection head 90. [Figure 6] FIG. 6 shows a quartz injection head 90 with a large number of regularly arranged holes that satisfy formula (C). FIG. 6(A) shows a plan view of the quartz injection head 90. FIG. 6(B) is a missing number. FIG. 6(C) shows a cross-sectional view taken along the arrow B--B. FIG. 4(D) shows a perspective view of the quartz injection head 90. [Figure 7]FIG. 7 is a reference diagram for the calculation method (part 1) of the airflow (plasma flow). [Figure 8] Figure 8 is a reference diagram for the airflow (plasma flow) calculation method (part 2). Figure (A) shows a perspective view of the airflow (plasma flow) calculation method (part 2). Figure (B) shows a cross-sectional view of the fluid flowing into a hole in a boron-containing quartz part 95 at an incident angle of θ (°). Figure (C) shows a view taken along the arrow AA in Figure (B), where the cross-sectional area of ​​the airflow = the cross-sectional area of ​​the hole = (π / 4)d2 (cm). [Figure 9] FIG. 9 is a diagram showing the relationship between the XYZ coordinate system and six views (front view, rear view, top view, bottom view, left side view, and right side view). [Figure 10] FIG. 10A is a perspective view of the quartz injection head 90. FIG. 10B is a front cross-sectional view of a boron-containing quartz part 95. The top view of FIG. 10B shows a front cross-sectional view of the boron-containing quartz part 95 that satisfies formula (A). The middle view of FIG. 10B shows a front cross-sectional view of the boron-containing quartz part 95 that satisfies formula (B). The bottom view of FIG. 10B shows a front cross-sectional view of the boron-containing quartz part 95 that satisfies formula (C). [Figure 11] 11A is a front view of the invention showing the range of the chamber CB (the range indicated by the thick diagonal lines), and FIG. 11B is an enlarged view of the front view of the invention showing the gap 10 and the quartz injection head 90 and its surroundings. [Explanation of symbols]

[0010] BD...Boron-containing diamond 100...Boron-containing diamond film manufacturing equipment G0... Deposition gas S0...film deposition gas intake port G1: Boron-containing gas S1...Boron-containing gas intake port G2...Exhaust gas E...Exhaust port CB...Chamber CB1...Cylinder-shaped chamber CB2...Dish-shaped chamber P0... Circuit board P01……Filming table 90...Quartz injection head 95...Boron-containing quartz parts 10...gap

Claims

1. A method for producing a boron-containing diamond film using the MPCVD method, in which a film-forming gas G0 is supplied from a film-forming gas inlet S0, an exhaust gas G2 is discharged from an exhaust port E, and a boron-containing diamond BD is formed on a substrate P0, characterized in that the film-forming gas G0 is supplied from a film-forming gas inlet S0, and a boron-containing quartz part 95 constituting a quartz injection head 90 is used as a boron doping element source.

2. 2. The method for producing a boron-containing diamond film according to claim 1, wherein the film-forming gas G0 is a mixed gas of methane gas and hydrogen gas.

3. A method for producing a boron-containing diamond film as described in claim 1, characterized in that a quartz injection head (90) consisting of a boron-containing quartz part (95) is installed on a film formation table (P01) at the center of the chamber (CB), the top of the quartz injection head (90) is adjacent to the top of the chamber (CB), and the gap (10) is less than 1 mm.

4. 4. The method for producing a boron-containing diamond film according to claim 3, wherein the diameter d (cm) and the diameter position r (cm) of the quartz injection head 90 satisfy the formula (A). d=C1 / r...Formula (A) Here, the aperture position r refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). C1 is a constant (cm ２ )

5. 4. The method for producing a boron-containing diamond film according to claim 3, wherein the diameter d (cm) of the hole of the quartz injection head 90 satisfies the following formula (B). d=const. ...Formula (B) Here, "const." means a constant (cm).

6. 4. The method for producing a boron-containing diamond film according to claim 3, wherein the diameter d (cm) of the hole of the quartz injection head 90 satisfies the following formula (C). d=C2 / cos(θ)...Formula (C) Here, θ refers to the angle of incidence (°). C2 refers to a constant (cm).

7. A boron-containing diamond film-forming manufacturing apparatus 100 utilizing an MPCVD apparatus 99 for forming a boron-containing diamond film on a substrate P0, the apparatus 100 being characterized by comprising a film-forming gas inlet S0 for supplying a film-forming gas G0, an exhaust port E for discharging an exhaust gas G2, and a boron-containing quartz part 95 constituting a quartz injection head 90 as a boron-doping element source.

8. 8. The boron-containing diamond film manufacturing apparatus 100 according to claim 7, wherein the film-forming gas G0 is a mixed gas of methane gas and hydrogen gas.

9. A boron-containing diamond film formation manufacturing apparatus 100 as described in claim 7, characterized in that a quartz injection head 90 consisting of a boron-containing quartz part 95 is installed on a film formation table P01 at the center of the chamber CB, the top of the quartz injection head 90 is adjacent to the top of the chamber CB, and the gap 10 is less than 1 mm.

10. The boron-containing diamond film forming manufacturing apparatus 100 according to claim 9, characterized in that the diameter d (cm) and the diameter position r (cm) of the hole of the quartz injection head 90 satisfy the formula (A). d=C1 / r...Formula (A) Here, the aperture position r refers to the distance (cm) from the center O of the quartz injection head 90 to the center of the hole of the quartz injection head 90 with an aperture d (cm). C1 is a constant (cm ２ )

11. 10. The boron-containing diamond film manufacturing apparatus 100 according to claim 9, wherein the diameter d (cm) of the hole of the quartz injection head 90 satisfies the formula (B). d=const. ...Formula (B) Here, "const." means a constant (cm).

12. 10. The boron-containing diamond film manufacturing apparatus 100 according to claim 9, wherein the diameter d (cm) of the hole of the quartz injection head 90 satisfies the formula (C). d=C2 / cos(θ)...Formula (C) Here, θ refers to the angle of incidence (°). C2 refers to a constant (cm).

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