JP2021134412A - Covering material including bcn coating or bcno coating and method for manufacturing the same - Google Patents

Abstract

To provide: a first covering material including a BCN coating excellent in adhesion with a base material; a second covering material including a BCNO coating showing fluorescence properties in ultraviolet irradiation; and a method for manufacturing the first or second covering material.SOLUTION: A first covering material includes a base material and a BCN coating covering at least a part of the surface thereof, and a second covering material including the base material and a BCNO coating covering at least a part of the surface thereof and exhibits fluorescence in ultraviolet irradiation. The BCNO coating has a layered structure having a layer interval of 0.34 nm and each layer is parallel to the base material in a region of 10 nm or more; the first covering material is manufactured by staying the evaporated material of an organic compound including boron atoms on the surface of the base material to irradiate the evaporated material with a laser having 30 W/cm2 or more; and the second covering material is manufactured by annealing the first covering material in an atmosphere in which oxygen exists or staying the mixture of the evaporated material of the organic compound including boron atoms and an oxidation gas on the surface of the base material to irradiate the mixture with the laser having 30 W/cm2 or more.SELECTED DRAWING: Figure 10

Description

The present invention relates to a coating material having a BCN coating or a BCNO coating, and a method for producing the same. More specifically, the present invention relates to a coating material having a hard BCN coating having excellent adhesion to a substrate, a coating material having a BCNO coating exhibiting fluorescence characteristics under ultraviolet irradiation, and a method for producing them.

Hexagonal boron nitride (h-BN) has a crystal structure similar to graphite, and has a structure in which an atomic layer composed of a six-membered ring lattice of boron atoms and nitrogen atoms is laminated. Boron nitride is a wide-gap semiconductor (electric insulator). It is also used as a semiconductor substrate and a dielectric material with high thermal conductivity. Boron nitride (BCN) in which a part of B or N of h-BN is replaced with carbon has an intermediate property between electrically conductive graphite and h-BN of an electric insulator.

BCN is useful as a hard coating or sliding member for semiconductor devices, optical components, and cutting tools. Further, as a fluorescent material, it is theoretically predicted that the fluorescence wavelength can be adjusted by changing the composition of BCN, but the full-color fluorescence characteristic has not been experimentally expressed, and the emission intensity (quantum). Efficiency) is also low (see, for example, Non-Patent Document 1).

A thin film form is desirable for semiconductor devices, hard coating applications, miniaturization and high efficiency of optical components, and fabrication of inorganic LEDs.

A method for producing a boron nitride material such as BN or BCN by sublimating an aminoboran complex on a base material is disclosed (see, for example, Patent Document 1). The BN and BCN described in Patent Document 1 are in the form of nanotubes. Further, a method for producing a porous boron nitride material is shown by sublimating an aminoboran complex and then annealing it in an environment containing oxygen.

A chemical vapor deposition method (CVD) or a physical vapor deposition method such as a pulse laser deposition method or a sputtering method is used to prepare a dense BCN film. In CVD, it is common to use boron trichloride (BCl ₃ ) or diborane as a boron raw material, ammonia as a nitrogen raw material, and a hydrocarbon gas such as acetylene or methane or carbon tetrachloride as a carbon raw material.
However, these raw materials have a high risk of explosiveness, corrosiveness, and flammability, and ensuring handleability and safety is an issue. In addition, the production and R & D environment is severely restricted due to the complicated equipment required to combine multiple high-risk gases and the indispensable abatement equipment, making it simpler and reducing the environmental load and danger. A manufacturing process is required.

As a method for producing BCN that does not use diborane or chloride as a CVD raw material, it is disclosed that an organic compound can be used as a raw material for boron, carbon, and nitrogen, and a BCN film can be produced by plasma CVD (see Non-Patent Document 2). ).
However, in general, plasma CVD contaminates not only the base material but also the inner wall of the manufacturing apparatus or the equipment inside the apparatus, so that it is difficult to maintain and manage the apparatus such as cleaning the inside of the furnace.

Boron nitride (BCNO) obtained by adding oxygen to BCN emits light under ultraviolet irradiation (it is a phosphor). It is disclosed that BCNO has a high quantum efficiency, the emission wavelength can be controlled by changing the composition ratio of B and C, and it is a fluorescent material containing no rare earth metal (see, for example, Non-Patent Document 3). So far, a molded body of BCNO in which the powder is solidified with a resin or the like has been produced.

Generally, fluorescent materials used for displays and LEDs contain rare earth metals and transition metals that serve as light emitting centers. A fluorescent material that does not contain a metal element, such as BCNO, is an elemental strategically advantageous fluorescent material that has little impact on the environment and the human body and has a low resource risk.
Therefore, these BCN and BCNO thin films and their manufacturing processes can be expected to enhance the functionality of semiconductor parts, optical parts, hard / wear-resistant parts, various phosphors, inorganic LEDs, etc., and reduce the human body / environmental load.

Japanese Patent Application Laid-Open No. 2019-503326 "Boron Nitride Material and Method for Manufacturing The Boron Nitride Material"

Watanabe et al., Phys. Rev. Lett. 77 (1996) p. 187 Kida et al., Vacuum 83 (2009) p. 1143-1146 Ogi et al., Adv. Mter. 20 (2008) p. 3235-3238 B. J. Matsoso et al., New J. et al. Chem. 41 (2017) p. 9497-9504.

So far, BCNO coatings have been produced by the CVD method, but the film thickness is as thin as several nm, and no one showing fluorescence characteristics is found.
Here, a method for producing a BCNO film by CVD using methane, boric acid, and ammonia as raw materials is disclosed (see, for example, Non-Patent Document 4). According to Non-Patent Document 4, the film thickness of BCNO is 10 nm or less, and there is no description regarding the fluorescence characteristics.

The present invention has been made in view of the above problems, and is a first coating material having a BCN coating which is a hard material and is a precursor of BCNO, and a second coating having a BCNO coating which exhibits fluorescence characteristics under ultraviolet irradiation. It is an object of the present invention to provide materials and methods for producing them. Another object of the present invention is to provide a method for producing a coating material, which has an effect of reducing an environmental load and a risk.

The present inventors have studied a base material, a coating material having an inorganic coating arranged on the surface thereof, and a method for manufacturing the same in optical parts, semiconductor parts, hard / wear-resistant parts, etc., and completed the present invention. I came to do it.
The means for solving the above problems are as follows.
[1] The first coating material of the present invention comprises a base material and a BCN coating that covers at least a part of the surface of the base material, and is characterized in that it does not emit fluorescence under ultraviolet irradiation.
[2] In the first coating material of the present invention, the oxygen content of the BCN coating can be less than 5 atomic%.
[3] The second coating material of the present invention comprises a base material and a BCNO coating film that covers at least a part of the surface of the base material, and is characterized in that it emits fluorescence under ultraviolet irradiation.
[4] In the second coating material of the present invention, assuming that the oxygen content on the outermost surface of the BCNO coating is 5 atomic% or more and B _x C _y N _z O _(1-x-y-z) . The B-atom molar ratio (x) is 0.2 to 0.7, the C-atom molar ratio (y) is 0.01 to 0.6, the N-atom molar ratio (z) is 0.1 to 0.6, and O atoms. The molar ratio (1-x-yz) can be 0.05 to 0.5.
[5] In the second coating material of the present invention, the BCNO coating has a layered structure having a layer spacing of 0.5 nm or less in cross-sectional microstructure observation, and the surface of each layer is parallel to the substrate in a region of at least 10 nm or more. Can be placed in.
[6] In the second coating material of the present invention, the BCNO coating can have a fluorescence characteristic of an emission wavelength of 400 to 800 nm under irradiation with an excitation wavelength of 200 to 450 nm.
[7] In the method for producing the first coating material of the present invention, the vaporized product of an organic compound containing a boron atom is retained on the surface of the base material in a state where a gas containing an oxygen atom is not supplied. It is characterized by irradiating a laser having a power density of 30 W / cm ^{2 or more.}
[8] In the method for producing the second coating material of the present invention, the first coating material can be produced by an annealing treatment in an atmosphere in which oxygen is present under air or reduced pressure.
[9] In another method for producing the second coating material of the present invention, a mixture of a vaporized substance of an organic compound containing a boron atom and an oxidizing gas is retained on the surface of a base material, and the power density is applied to the vaporized substance. It is characterized in that it is produced by irradiating a laser of 30 W / cm ^{2 or more.}

Since the first coating material of the present invention has a hard BCN coating on the surface of the base material, it is useful as a coating for optical parts, semiconductor parts, cutting tools, and a sliding member. It is also useful as a precursor for the second coating material of the present invention.
The second coating material of the present invention has a layered and dense BCNO coating having excellent adhesion to the substrate, and can exhibit fluorescence characteristics under ultraviolet irradiation. Therefore, it is suitable as an optical component, a semiconductor component, an inorganic LED, or a light emitting element.
Further, in the method for producing the first coating material and the second coating material of the present invention, it is not necessary to set the entire inside of the film forming chamber to a high temperature, and the film forming chamber which has been conventionally known as a defect of CVD. It is possible to suppress the formation of a film on the inner wall of the substrate and to form a dense inorganic film having excellent adhesion at a predetermined position of the base material, and it is possible to reduce the environmental load and the risk.

(A) is a schematic explanatory view showing an example of the first coating material, and (b) is a schematic cross-sectional view taken along the line AA of (a). It is a scanning electron microscope image (5000 times) of the surface which ion-polished the cross section of the 1st coating material obtained in Example 1. FIG. It is a scanning electron microscope image (10000 times) of the surface of the first coating material obtained in Example 1. It is a scanning electron microscope image (10000 times) of the fracture surface of the first coating material obtained in Example 2. 6 is a scanning electron microscope image (10000 times) of the surface of the first coating material obtained in Example 2. It is a scanning electron microscope image (2500 times) of the fracture surface of the first coating material obtained in Example 3. It is a scanning electron microscope image (10000 times) of the surface of the first coating material obtained in Example 3. (A) is a schematic explanatory view showing an example of the second covering material, and (b) is a schematic BB sectional view of (a). It is a transmission electron microscope bright-field image (40,000 times) of the cross section in the vicinity of the surface of the second coating material obtained in Example 5. It is a transmission electron microscope bright-field image (500,000 times) of the cross section in the vicinity of the surface of the second coating material obtained in Example 5. The lower left is a selected area electron diffraction image of the region. 3 is an excitation and fluorescence spectrum of the second coating material obtained in Example 5. 6 is an excitation and fluorescence spectrum of the second coating material obtained in Example 6. It is a fluorescence spectrum of the second coating material obtained in Example 7. 8 is an excitation and fluorescence spectrum of the second coating material obtained in Example 8. It is explanatory drawing which shows an example of the manufacturing apparatus of a covering material.

[1] First Coating Material As shown in FIG. 1, the coating material 10 of the present invention includes a base material 20 and a BCN coating 30 that covers at least a part of the surface 20a of the base material 20. It is characterized in that it does not emit fluorescence under ultraviolet irradiation. In this specification, when a numerical range or the like is indicated by using "~", the numerical values or the like at both ends thereof are included.

The "base material 20" is an object to be coated with the BCN coating 30. The material of the base material 20 has heat resistance that does not melt and decompose at at least 300 ° C., and further, from a material that does not react with boron, nitrogen, carbon and oxygen, which are elements constituting the film, at 400 ° C. to 2000 ° C. As long as it is, there is no particular limitation. The constituent material of the base material 20 is preferably an inorganic material (ceramics, metal, alloy, etc.), for example, carbon (C), silica (SiO ₂ ), alumina (Al ₂ O ₃ ), YAG (Y ₃ Al). ₅ O ₁₂ ), zirconia (ZrO ₂ ), silicon carbide (SiC), silicon nitride (Si ₃ N ₄ ), gallium nitride (GaN), silicon (Si), carbon, fiber-reinforced carbon composite material (C _f / C) , Fiber-reinforced SiC composite material (SiC _f / SiC) and the like.
It should be noted that these may be used alone or in combination of two or more.

The shape of the base material 20 is not particularly limited, and may be plate-like, linear, lump-like, or the like, and the surface 20a of the base material 20 having the BCN coating 30 may be either a flat surface or a curved surface, and further. The surface may be smooth and may have recesses or protrusions.

The BCN constituting the "BCN coating 30" is boron nitride composed of boron, carbon and nitrogen, and is generally represented by "BCN". Boron (B), carbon (C), and nitrogen (N) can adopt various composition ratios, _{and thus can be expressed as, for example, B x} C _y N _z (where x + y + z = 1).
Assuming that B _x C _y N _z , in the present invention, the B atomic molar ratio (x) is 0.2 to 0.6 and the C atomic molar ratio (y) is 0.1 to 0 on the outermost surface of the BCN coating 30. .7, the N-atom molar ratio (z) is preferably 0.1 to 0.6. x, y, either z, or more is less than 0.1, boron nitride (BN), since the boron carbide _(B 4 C) or carbon (C) near the composition and crystal structure, oxygen is present It is difficult to obtain BCNO by annealing treatment in an atmosphere (not useful as a precursor of BCNO). Here, the "outermost surface" is a surface that can be scraped by subjecting the surface of the first coating material to 3 kV Ar ion sputtering treatment (sputtering rate for silica is 20 nm / min) for a maximum of 40 minutes. It is defined as a depth range of 1 μm or less. Further, the BCN constituting the "BCN coating 30" does not substantially contain a transition metal element and a rare earth metal element. Here, "substantially free of an element" means that a peak derived from the element is not observed in the photoelectron spectroscopic analysis measurement.
The oxygen content as an impurity in the BCN coating made of boron nitride is less than 5 atomic% on the outermost surface when the entire BCN coating is 100 atomic%, and even if it is constant in the entire BCN coating, the cross-sectional direction May be different. In the latter case, the oxygen content in all parts of the BCN coating is preferably less than 5 atomic%, more preferably 3 atomic% or less, still more preferably 2 atomic% or less. The lower the oxygen content, the higher the hardness of the BCN coating, and the more excellent the hard material as the coating material can be provided.

In the first coating material 10 of the present invention, the thickness of the BCN coating 30 is preferably 10 nm or more, more preferably 100 nm, because it is useful as an optical component, a semiconductor component, and a hard / wear-resistant component suitable for various applications. It is ~ 1 mm, more preferably 200 nm ~ 100 μm. Further, there are no voids or cracks at the interface between the BCN coating 30 and the base material 20, and it is preferable that they are in close contact with each other.

[2] Second Coating Material As shown in FIG. 8, the second coating material 40 of the present invention includes a base material 20 and a BCNO coating material 50 that covers at least a part of the surface 20a of the base material 20.
The "coating" includes a case where the BCNO coating 50 adheres to the surface 20a of the base material 20 and directly coats the coating, and also indirectly covers the coating through the BCN coating 30 formed on the surface 20a of the base material 20. Including the case.
The second coating material 40 is characterized in that it emits fluorescence under ultraviolet irradiation.
The “base material 20” is the same as the base material of the first coating material 10, and is as described above.

The BCNO constituting the "BCNO coating 40" is boron nitride composed of boron, carbon, nitrogen, and oxygen, and is generally represented by "BCNO". Boron (B), carbon (C), nitrogen (N), and oxygen (O) can adopt various composition ratios. Therefore, for example, B _{x Cy} N _z O _(1-x-yz). It can be expressed as.
Assuming that B _x C _y N _z O ( _1-x-y-z) , in the present invention, the B atomic molar ratio (x) is 0.2 to 0.7 on the outermost surface of the BCNO coating 40, and the C atomic molars. It is preferable that the ratio (y) is 0.1 to 0.6, the N atomic molar ratio (z) is 0.1 to 0.6, and the O atomic molar ratio (1-x-yz) is. The B-atom molar ratio (x) is 0.2 to 0.7, the C-atom molar ratio (y) is 0.01 to 0.6, the N-atom molar ratio (z) is 0.1 to 0.6, and O atoms. The molar ratio (1-x-yz) is preferably 0.05 to 0.5. Here, the "outermost surface" is a surface that can be scraped by subjecting the surface of the second coating material to 3 kV Ar ion sputtering treatment (sputtering rate for silica is 20 nm / min) for a maximum of 40 minutes. It is defined as a depth range of 1 μm or less. Further, the BCNO constituting the BCNO coating 40 does not substantially contain a transition metal element and a rare earth metal element. Here, "substantially free of an element" means that a peak derived from the element is not observed in the photoelectron spectroscopic analysis measurement. The BCNO coating on the second coating material 40 may be either amorphous or crystalline. It may be translucent, and may be white to black or colored.

In the BCNO coating film 50 of the second coating material 40, as shown schematically in FIG. 8, layers 501 and 502 are formed in parallel with the surface (film-forming surface) 20a of the base material 20, and the BCNO coating film 50 is formed in layers with a layer spacing W. Has been done.
As shown in FIG. 10, in the transmission electron microscope (TEM) observation of the cross section of the coating film 50 in the direction perpendicular to the surface 20a of the base material 20, the layer spacing W is 0.5 nm or less at an observation magnification of 100,000 times or more. It is confirmed that the surface of each layer is arranged in parallel with the surface of the base material 20a.
Generally, in BCNO particles produced by powder synthesis, it is considered that the origin of light emission is a random layer structure of boron nitride in which oxygen and nitrogen are solid-solved (layer spacing is about 0.34 nm). The directions of the layer structures in such BCNO particles are aligned in a region of about several nm, but the directions of the layers are not aligned in a size of 10 nm or more.
On the other hand, the BCNO coating film in the present invention has a uniform layer structure in a region of at least 10 nm or more when observed with a transmission electron microscope. Such a BCNO coating having directionality in the layer structure that is the origin of light emission can be expected to have excellent fluorescence characteristics such as high luminous efficiency and directivity.

The BCNO coating in the second coating material of the present invention exhibits fluorescence (photoluminescence) under ultraviolet irradiation. The excitation wavelength is not particularly limited as long as it is in the visible region from ultraviolet to short wavelength, and is preferably 200 nm to 450 nm, for example. The emission wavelength can be adjusted from 400 nm to 800 nm depending on the composition of the inorganic film.

In the second coating material of the present invention, the thickness of the BCNO coating film in the vertical direction with respect to the surface 20a of the base material 20 is preferably 10 nm or more, more preferably 10 nm or more because it is useful as a light emitting element or a phosphor suitable for various applications. Is 100 nm to 1 mm, more preferably 200 nm to 100 μm.

[3] Method for Producing First Coating Material The method for producing the first coating material in the present invention is referred to as an organic compound containing a boron atom (hereinafter, referred to as "boron atom-containing organic compound") in a state where a gas containing an oxygen atom is not supplied. ) Is retained on the surface 20a of the base material 20, and the vaporized compound is irradiated with a laser having a ^{power density of 30 W / cm 2 or more.}
That is, this manufacturing method can be said to be a method of manufacturing the covering material 10 by forming a BCN coating 30 that covers at least a part of the surface 20a of the base material 20.

In the method for producing the first coating material in the present invention, only a vaporized product of a boron atom-containing organic compound is used as a raw material gas. Conventionally, when an inorganic film made of ceramics is produced by known CVD, it has been common to use a plurality of raw material components (diborane, halogen compound, hydrocarbon, hydrogen, ammonia, etc.) for forming the inorganic film.
On the other hand, in the method for producing the first coating material of the present invention, a BCN film can be formed by one kind of raw material component, that is, a boron atom-containing organic compound.
Further, the BCN coating 30 in the present invention is formed in a closed space as in the conventional CVD method. In the conventional CVD method, when a plurality of raw material components as described above are mixed and reacted with each other, the inner wall of the manufacturing apparatus or the equipment in the apparatus is contaminated. Since the material is locally heated and a film is formed, the above-mentioned problems are suppressed.

The boron atom-containing organic compound is not particularly limited as long as it vaporizes without decomposition at the boiling point. The boron atom-containing organic compound is a compound containing a carbon atom, a nitrogen atom and a boron atom, and is preferably a compound that vaporizes at a temperature of 0 ° C. to 250 ° C.
In the present invention, a compound containing a carbon atom, a nitrogen atom, a hydrogen atom and a boron atom is particularly preferable, and this compound is also preferable because it does not generate a corrosive gas after vaporization.
A boron atom-containing organic compound containing a carbon atom, a hydrogen atom, a nitrogen atom and a boron atom is preferably a general formula: B (NC _n H _{2n + 1 Cm} H _{2m + 1} ) ₃ (in the formula, n is an integer of 1 to 5). m is an integer of 1 to 5) or B ₂ (NC _n H _{2n + 1} C _m H _{2m + 1} ) ₄ is a tetrakis (alkylamide) diboron. The tetrakis (alkylamide) boron includes _{tri (ethylmethylamide) boron represented by B (NCH 3} C ₂ H ₅ ) ₃ , tri (dimethylamide) boron, tri (diethylamide) boron, and tetrakis (ethylmethylamide). ) Diboran, tetrakis (dimethylamide) diboran, tetrakis (diethylamide) diboran and the like, and among these, tetrakis (dimethylamide) diboran is preferable.

The method for preparing the vaporized product of the boron atom-containing organic compound is not particularly limited, and conventionally known heating methods, vaporization methods by bubbling method, and the like are applied.
The vaporized product of the boron atom-containing organic compound used in the method for producing the first coating material may be only one type or two or more types. In addition to the above-mentioned boron atom-containing organic compounds, vaporized compounds of N-containing machine compounds such as _{urea (CH 4} N ₂ O) and hexamethylenetetramine (C ₆ H ₁₂ N _{4) and gases such as hydrogen and ammonia.} May be added.

In the method for producing the first coating material, the vaporized product of the boron atom-containing organic compound is retained on the surface of the base material before the laser irradiation. The retention may be carried out in any way, but usually, the vaporized product of the boron atom-containing organic compound is placed in a film-forming chamber (usually, a space sealed so that the pressure can be adjusted. The film-forming device will be described later. ) Can be realized.
In a state where a gas containing an oxygen atom is not supplied, a gas flow containing a vaporized product of an organic compound containing a boron atom is retained on the surface of the base material, and the power density of the vaporized product is 30 W / cm ² or more. It is characterized by irradiating a laser.
The method of supplying the vaporized product is not particularly limited, and the film formation can be stably promoted by continuous supply or intermittent supply. When supplying the vaporized product, a method using a carrier gas (inert gas), a method of flowing the vaporized product by evacuation, and the like can be mentioned. The supply rate of the vaporized product (linear velocity of the gas flow) is preferably 0.01 to 100 cm / sec, more preferably 0.1 to 10 cm / sec.
The film-forming environment (environment for forming the film 30) is not limited, but it is preferable to use a reduced pressure environment. The pressure in the film forming chamber at the time of depressurization is not particularly limited, but is preferably 20 to 10000 Pa, more preferably 100 to 2000 Pa. Before supplying the vaporized product to the membrane-forming chamber, the membrane-forming chamber is decompressed in advance, and the oxygen partial pressure is preferably 50 Pa or less to suppress the influence of oxygen gas, water, etc., and the oxygen content. The coating material 10 having the BCN coating film 30 made of boron nitride having a value of less than 5 atomic% can be efficiently produced.

In the method for producing the first coating material in the present invention, the vaporized product of the boron atom-containing organic compound is irradiated with a laser in a state of being retained on the surface of the base material.
The laser used is not particularly limited, but a semiconductor laser, a solid-state laser, a gas laser, or the like can be used. Only one of these may be used, or two or more thereof may be used in combination. Further, the oscillation mode is not limited, and either continuous oscillation or pulse oscillation may be used, but continuous oscillation is preferable. The wavelength of the oscillated laser light is also not limited, but is usually 100 to 10800 nm.
Preferred lasers include an excima laser (wavelength: 193 to 351 nm), an Nd: YAG laser (wavelength: 1064 nm), a semiconductor laser using indium gallium arsenic phosphorus or aluminum gallium arsenic (wavelength: 800 to 900 nm), and a carbon dioxide gas laser (wavelength: 800 to 900 nm). Wavelength: 10.8 μm), fiber laser (wavelength: 1604 nm) and the like. Only one of these may be used, or two or more thereof may be used in combination. Of these, Nd: YAG lasers and semiconductor lasers are preferable.

The power density of the laser that irradiates the vaporized product of the boron atom-containing organic compound is 30 W / cm ² or more, preferably ^{30 to 500 W / cm 2} , more preferably 40 to 200 W, because a dense inorganic film can be obtained. / Cm ² . When irradiated with a laser having such a power density, the temperature on the film-forming surface of the base material is usually 800 ° C. to 1300 ° C. The power density of the irradiating laser may be constant or may be changed from beginning to end.

The laser irradiation time is appropriately selected depending on the film-forming area, the thickness of the BCN film 30, and the like, but is usually 1 minute to 60 minutes. When forming a large-area film, the method of irradiating the laser while scanning the laser with the base material 20 fixed or changing the optical path through a light diffusing lens, or the optical path while moving the base material 20. A method of irradiating a fixed laser can be applied.

The atmosphere when irradiating the laser is preferably an inert gas atmosphere or a vacuum in which the coexistence of gas containing oxygen atoms is suppressed. When an inert gas is used, argon, helium, nitrogen and the like are preferable. When the atmosphere is an inert gas, the pressure is preferably 0.01 to 10000 Pa, more preferably 20 to 10000 Pa.

When irradiating with a laser, it is preferable to preheat the base material 20 from the viewpoint of efficient film formation. The preheating temperature of the base material 20 is preferably 200 ° C. or higher, more preferably 400 ° C. or higher. For example, a method of preheating using an infrared lamp, a halogen lamp, or the like, a method of preheating by using resistance heating, high frequency induction heating, microwave heating, or the like can be mentioned. As these preheating means, only one type may be used, or two or more types may be used in combination.
You may use it.

When a vaporized product of a boron atom-containing organic compound is retained on the surface of a base material and irradiated with a laser, the boron atom-containing organic compound is decomposed to produce boron nitride. Before the vaporized product of the boron atom-containing organic compound is retained on the surface of the base material, it is preferable to reduce the pressure inside the film forming chamber 61 and maintain the oxygen partial pressure at 50 Pa or less. Then, when the temperature rise is saturated, film formation is started, and a dense BCN film made of boron nitride having an oxygen content of less than 5 atomic% is formed.

The manufacturing apparatus 60 used in the method for manufacturing the first coating material in the present invention is not particularly limited, but as shown in FIG. 15, at least the film forming chamber 61, the raw material gas supply means 63, the laser irradiation means 67, and the like. It is preferable to provide.

The film-forming chamber 61 is a space on which the base material 20 can be placed, and provides a space for forming a film-forming environment. The film forming chamber 61 is usually connected to a raw material gas supply means 63 for supplying a vaporized product of a boron atom-containing organic compound into the film forming chamber 61. Further, it is optically connected to the laser irradiation means 67 so that the base material 20 placed in the film forming chamber 61 can be irradiated with the laser.
Further, a temperature measuring device 68 can be installed outside the film forming chamber 61 so that the surface temperature of the base material 20 can be measured (non-contact measurement). In this case, the measurement can be performed through the window material 681 of the film forming chamber 61.

The raw material gas supply means 63 is a means for supplying a vaporized product of a boron atom-containing organic compound into the film forming chamber 61. The configuration of the raw material gas supply means 63 is not limited, but for example, the raw material gas preparing means 64 for adjusting the vaporization of the boron atom-containing organic compound can be provided.
More specifically, the raw material gas adjusting means 64 accommodates a storage tank 641 containing a boron atom-containing organic compound before vaporization and other organic compounds before vaporization (for example, a nitrogen atom-containing compound such as urea). A storage tank 642 and a heater 643 for heating each of these storage tanks 641 and 642 to form a vaporized product of these compounds can be provided.
The number of storage tanks is not limited, and a storage tank for mixing other types of raw materials may be provided.

The raw material gas supply means 63 is a carrier gas supply means 651 and a mass flow rate in order to appropriately supply a predetermined amount of the vaporized product of the boron atom-containing organic compound produced in the raw material gas preparation means 64 to the film forming chamber 61. A controller 631 can be provided.
Further, as will be described later, when the oxidation gas is used in the production of the second coating material 40, the oxidation gas supply means 652 and the mass flow controller 632 can be provided. Further, the flow rate control of these vaporized substances, the oxidizing gas and the like can also be performed by using the depressurizing means 62. That is, these various means can be used in combination.

When the carrier gas supply means 651 is used, the carrier gas supply means 651 may be arranged on the upstream side of the raw material gas preparing means 64, may be arranged on the downstream side of the raw material gas preparing means 64, or these. It may be placed in both. Similarly, the oxidation gas supply means 652 may be arranged on the upstream side of the raw material gas preparing means 64, may be arranged on the downstream side of the raw material gas preparing means 64, or may be arranged on both of them. good.

The laser irradiation means 67 is provided at a predetermined location in the film forming chamber 61 (for example, the base material support base 6 described later).
It is a means capable of irradiating a laser toward the surface 20a) of the base material 20 placed on the 9. Usually, the laser irradiation means 67 is installed outside the film forming chamber 61, and is configured so that the laser can be irradiated into the film forming chamber 61 through the window material 672 of the film forming chamber 61.
Further, as described above, the laser irradiation means 67 can be provided with a mechanism capable of changing the laser irradiation location so as to correspond to a large area. FIG. 15 illustrates a mode in which the surface 20a of the base material 20 can be irradiated with the laser while changing the optical path through the light diffusing lens 671. The constituent material of the light diffusing lens 671 is not limited and may be appropriately selected depending on the type or wavelength of the laser, and for example, quartz, BK7, zinc selenide and the like can be used.
When a part of the base material 20 has a region not intended to form the coating film 30, it can be realized by covering this region, that is, by masking.

Further, the manufacturing apparatus 60 can have a depressurizing means 62 so that the environmental pressure in the film forming chamber 61 can be adjusted. The depressurizing means 62 can also be connected to the film forming chamber 61.
As the depressurizing means 62, a conventionally known vacuum pump or the like can be used. When the decompression means 62 is provided, it is preferable that the connection portion (raw material gas introduction port) of the film forming chamber 61 and the raw material gas supply means 63, the base material 20, and the decompression means 62 are arranged in a straight line.

Further, the manufacturing apparatus 60 can have a base material support base 69. The base material support base 69 is a support base on which the base material 20 is placed, and may be provided with a fixing mechanism for fixing the base material 20 as needed. Similarly, a moving mechanism for rotating or moving the base material 20 can be provided as needed. Further, the base material support base 69 can be provided with a preheating mechanism capable of preheating the base material 20.

[3] Method for Producing Second Coating Material The method for producing the second coating material 40 of the present invention includes (1) a method for producing the first coating material 10 by an annealing treatment (hereinafter referred to as "manufacturing method A"). (2) There is a method of producing by irradiating a laser with a mixture of a vaporized body of a boron-containing organic compound and an oxidizing gas retained on the surface of a base material (hereinafter referred to as "manufacturing method B").

(1) Manufacturing method A
The method A for producing the second coating material 40 is characterized in that the first coating material 10 is produced by an annealing treatment in an atmosphere in which oxygen is present under atmospheric pressure or reduced pressure. That is, the BCN coating 30 constituting the first coating material 10 is changed to the BCNO coating 50 constituting the second coating material 40 by performing an annealing treatment in an atmosphere in which oxygen is present in the atmosphere or under reduced pressure. ..
As the manufacturing method A, the first covering material 10 obtained by the above-mentioned manufacturing method of the first covering material is used. Since the method for producing the first covering material 10 is as described above, the description thereof will be omitted.
The method of the annealing treatment is not particularly limited, and can be performed by heating in a heating furnace in an oxidizing environment, heating by laser irradiation, induction heating, or the like.
The annealing temperature is 600 to 1200 ° C, preferably 750 to 1100 ° C. At a temperature lower than 600 ° C., oxidation does not proceed and BCNO having fluorescent characteristics is not produced. Further, at a temperature higher than 1200 ° C., the BCN film evaporates or oxidation proceeds too much _{and changes to boric acid (B 2} O ₃ ), boric acid (H ₃ BO ₃ ), etc., and does not show fluorescence characteristics.
When annealing is performed by laser heating, the manufacturing apparatus 60 of the first coating material 10 can be used as it is.
When laser heating is performed in the atmosphere, heating under atmospheric pressure can be performed by opening the raw material gas supply means 63 to the atmosphere as it is in the manufacturing apparatus 60.
Further, when laser heating is performed under reduced pressure, as shown in FIG. 15, the oxidation gas can be supplied from the oxidation gas supply means 652 via the mass flow controller 632. The flow rate control of the oxidizing gas can also be performed by using the depressurizing means 62. That is, these various means can be used in combination.
Further, annealing can also be performed by heat treatment in an electric furnace in the atmosphere. The first coating material 10 can be placed on a support base in an electric furnace (not shown) and can be performed at the same temperature and time as laser heating.

(2) Manufacturing method B
In the method B for producing the second coating material 40, a vaporized substance of a boron atom-containing organic compound and a gas containing an oxygen atom (hereinafter, referred to as “oxidizing gas”) are retained on the surface of the base material. It is characterized by irradiating the vaporized product with a laser.

As the manufacturing method B of the second covering material 40, a manufacturing method similar to the manufacturing method of the first covering material 10 can be adopted. That is, in the method for producing the first coating material 10, the raw material gas is only the vaporized product of the boron atom-containing organic compound, but in the method B for producing the second coating material 40, the raw material gas is the boron atom-containing organic compound. The difference is that a vaporized compound obtained by further mixing an oxidizing gas with the vaporized compound is used. Other than that, the manufacturing method and manufacturing apparatus of the first covering material 10 can be adopted, which are substantially the same as those of the manufacturing apparatus 60.

The method for preparing the vaporized product of the boron atom-containing organic compound is not particularly limited, and conventionally known heating methods, vaporization methods by bubbling method, and the like are applied. The vaporized product of the boron atom-containing organic compound used in the production method B may be only one type or two or more types.
In addition to the boron atom-containing organic compound, vaporized products of N-containing organic compounds such as _{urea (CH 4} N ₂ O) and hexamethylenetetramine (C ₆ H ₁₂ N _{4) and gases such as hydrogen and ammonia are added.} You may.
Before irradiating the laser, a mixture of a vaporized product of a boron atom-containing organic compound and an oxidizing gas is retained on the surface of the substrate. The method of supplying the mixture is not particularly limited, and the film formation can be stably promoted by continuous supply or intermittent supply. When supplying the mixture, a method using a carrier gas (inert gas), a method of flowing the mixture by evacuation, and the like can be mentioned.
The oxidation gas is not particularly limited, but is _{a vaporized product of oxygen (O 2} ), carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), urea (CH ₄ N ₂ O) and the like. Is preferable.
The supply rate (linear velocity of the gas flow) of the mixture of the vaporized product and the oxidizing gas is preferably 0.01 to 100 cm / sec, more preferably 0.1 to 10 cm / sec.
Further, in the production method B, a method of forming a film under reduced pressure conditions is preferable. The pressure at the time of depressurization is preferably 20 to 10000 Pa, more preferably 100 to 2000 Pa. As long as the vaporized product of the boron atom-containing organic compound and the oxidizing gas are a mixture of a predetermined ratio on the surface of the base material, these vaporized products may be separately supplied to the surface of the base material. good.

In the production method B, a mixture of a vaporized product of a boron atom-containing organic compound and an oxidizing gas is retained on the surface 20a of the base material 20, and the mixture is irradiated with a laser. The laser used is not particularly limited, and the laser used in the method for producing the first coating material can be applied.

Power density of the laser irradiated to the mixture of the vaporized material and the oxidizing gas of boron-containing organic compound, since the dense inorganic coating is obtained, and at 30 W / cm ² or more, preferably 40~500W / cm ^2, more It is preferably 50 to 200 W / cm ² . The power density of the laser irradiating the mixture may be constant or variable from beginning to end.

The laser irradiation time is appropriately selected depending on the film formation area, thickness, and the like of the BCNO film 50, but is usually 1 to 60 minutes.
The method of irradiating the laser, the atmosphere when irradiating the laser, and the preheating of the base material can be the same as in the method for producing the first coating material.

The second covering material 40 can be manufactured by the above manufacturing method B. That is, when a mixture of a vaporized product of a boron atom-containing organic compound and an oxidation gas is retained on the surface 20a of the base material 20 and irradiated with a laser, the boron atom-containing organic compound decomposes and reacts with oxygen atoms in the oxidation gas. BCNO (boron nitride oxycarbonate) containing oxygen is generated, and a dense BCNO film having fluorescent characteristics is formed on the surface 20a of the base material 20.

The manufacturing apparatus used in the method for producing the second covering material in the present invention is not particularly limited, but for example, the manufacturing apparatus 60 used for manufacturing the covering material 1 can be used.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to such examples as long as the gist of the present invention is not exceeded.

1. 1. Raw Material Compound Tetrakis dimethylaminodiborane (manufactured by Oakwood Co., Ltd., TDMAB, model number: 011060) was used as the boron atom-containing organic compound.

2. Base material As the base material, a synthetic quartz glass (SiO ₂ ) disk-shaped base material was used. The size is φ15 mm × 0.5 mm.

3. 3. Manufacturing Equipment In Examples 1 to 4 and Comparative Example 1 below, the following manufacturing equipment 60 shown in FIG. 15 was used.
The film forming chamber 61, the raw material gas supply means 63, the laser irradiation means 67, the raw material gas preparation means 64, and the carrier gas supply means 651 that constitute the manufacturing apparatus 60 are as described above.
In Examples 1 to 4 and Comparative Example 1, the following means and the like were particularly adopted.
The laser irradiation means 67 is provided with a light source that oscillates an Nd: YAG laser (wavelength: 1064 nm), and a lens 671 for adjusting the laser beam diameter is arranged. Further, the base material 20 was placed on a heat-resistant support base 69 capable of preheating the base material 20 on the extension of the optical path of the laser emitted from the laser irradiation means 67. The temperature when the surface 20a of the base material 20 was formed by irradiating the laser was measured using a temperature measuring device 68. Further, the inside of the film forming chamber 61 can be an inert gas atmosphere or a depressurized gas, but as a depressurizing means 62, an oil rotary vacuum pump is connected to the film forming chamber 61.

4. Production and Evaluation of First Coating Material (1) Example 1
Tetrakis dimethylaminodiborane was contained in the storage tank 641 and heated to 63 ° C. by a heater 643 to prepare a raw material gas.
Then, in the film forming chamber 61, the base material 20 (synthetic quartz glass) was placed on the support base 69, and the base material 20 was preheated to 300 ° C. Preheating was performed by resistance heating of the support base 69.
After that, in a state where the inside of the film forming chamber 61 is in a reduced pressure atmosphere (total pressure 20 Pa or less, oxygen partial pressure 4 Pa or less), the raw material gas is mixed with argon gas (carrier gas) at a flow rate of 50 sccm (linear speed 0.47 cm / sec). It was supplied to the film forming chamber 61, and the inside of the film forming chamber 61 was set to 200 Pa.
Then, a laser having a power density of 53 W / cm ² was applied to the surface 20a of the base material 20 for 15 minutes. The power density was calculated by dividing the output of the laser before it was incident on the light diffusing lens 671 and the window material 672 by the irradiation area. The temperature of the surface 20a of the base material 20 during film formation was 1100 ° C.
After that, while the depressurizing means 62 (oil rotary vacuum pump) was still in operation, the supply of the raw material gas was stopped, and then the laser irradiation was terminated. Then, after the internal pressure of the film forming chamber 61 is set to 50 Pa or less and the temperature of the surface 20a of the base material 20 is lowered to 400 ° C. or less, the decompression means 62 is stopped to open the film forming chamber 61 to atmospheric pressure. , The first coating material 10 of Example 1 was taken out from the film forming chamber 61.

The color of the BCN coating film 30 formed on the first coating material 10 of Example 1 is black, the thickness is 4.6 μm, and the film forming speed calculated from this thickness and the film forming time is 18.4 μm. / It was time. It was.
When the obtained BCN film 30 was subjected to X-ray diffraction measurement, it was found to be an amorphous film having a wide diffraction peak at 2θ = 23 to 28 °. Further, the composition of the BCN film 30 X-ray photoelectron spectroscopy (XPS, ULVAC-PHI, Inc., model "VersaProbe PHI5000", source: monochromatic AlK, 15kV, 25W, beam diameter: 100 [mu] m) was analyzed by, _{B 0 It was .38} C _0.37 N _0.25 , and no other metal elements were detected. At this time, in order to remove impurities on the outermost surface 30a of the BCN coating 30, a sputtering treatment with 3 kV Ar ions for 1 minute (sputtering rate for silica was 20 nm / min) was performed. The amount of oxygen in the BCN coating 30 was 1.6 atomic% when the entire BCN coating 30 was taken as 100%.
Further, the surface and cross section (fracture surface) of the BCN coating 30 were observed with a scanning electron microscope (manufactured by JEOL Ltd., the same applies hereinafter as model "JSM-IT300HR / LV"). Images of FIG. 2 (cross section of the first coating material 10) and FIG. 3 (surface image of the BCN coating 30) were obtained, respectively. Here, the fracture surface of the first coating material 10 in FIG. 2 was ion-polished (smoothed) by a cross-section polisher (CP, manufactured by JEOL Ltd., model "IB-1951CP") before observation. As shown in FIG. 2, it was observed that the BCN coating 30 of the first coating material 10 was dense and homogeneous, and was in close contact with the surface 20a of the base material 20. Further, as shown in FIG. 3, it was observed that a smooth surface structure was formed on the surface 30a of the BCN coating 30.

(2) Example 2
Same as in Example 1 except that the laser power density was 32 W / cm ² , the temperature of the substrate 20 surface 20a during film formation was 930 ° C, and the film formation time was 20 minutes under the film formation conditions of Example 1. The first coating material 10 was obtained. The color of the obtained BCN coating film 30 was black, the thickness was 2.6 μm, and the film forming speed calculated from this thickness and the film forming time was 7.8 μm / hour. When the obtained BCN film 30 was subjected to X-ray diffraction measurement, it was found to be an amorphous film having a wide diffraction peak at 2θ = 23 to 28 °. The surface and cross section (fracture surface) of the BCN coating 30 were observed with a scanning electron microscope. Images of FIG. 4 (cross section of the first coating material 10) and FIG. 5 (surface image of the BCN coating 30) were obtained, respectively. As shown in FIG. 4, it was observed that the BCN coating 30 of the first coating material 10 was dense and homogeneous, and was in close contact with the surface 20a of the base material 20. Further, as shown in FIG. 5, it was observed that a smooth surface structure was formed on the surface 30a of the BCN coating 30.

(3) Example 3
Under the film-forming conditions of Example 1, the raw material gas was prepared by heating to 64 ° C. with a heater 643, the power density of the laser was 63 W / cm ² , and the temperature of the base material 20 surface 20a during film-forming was 1150 ° C. Except for the above, the same operation as in Example 1 was carried out to obtain the first coating material 10. The color of the obtained BCN coating film 30 was black, the thickness was 5.2 μm, and the film forming speed calculated from this thickness and the film forming time was 20.8 μm / hour. When the obtained BCN film 30 was subjected to X-ray diffraction measurement, it was found to be an amorphous film having a wide diffraction peak at 2θ = 23 to 28 °. The surface 30a and the cross section (fracture surface) of the BCN coating 30 were observed with a scanning electron microscope. Images of FIG. 6 (fracture surface of the covering material 10) and FIG. 7 (surface image of the BCN coating) were obtained, respectively. As shown in FIG. 6, it was observed that the BCN coating 30 of the first coating material 10 was dense and homogeneous, and was in close contact with the surface 20a of the base material 20. Further, as shown in FIG. 7, it was observed that a smooth surface structure was formed on the surface 30a of the BCN coating 30.

(4) Example 4
Under the film-forming conditions of Example 1, the raw material gas was prepared by heating to 57 ° C. with a heater 643, the power density was 64 W / cm ² , the temperature of the substrate 20 surface 20a during film-forming was 1140 ° C., and film-forming. The same operation as in Example 1 was performed except that the time was set to 30 minutes, and the first coating material 10 was obtained. The color of the obtained BCN film 30 was black, and when it was subjected to X-ray diffraction measurement, it was found to be an amorphous film having a wide diffraction peak at 2θ = 23 to 28 °.

(5) Comparative Example 1
In the film forming conditions of Example 1, the power density of the laser was 28 W / cm ² , the temperature of the substrate 20 surface 20a during film forming was 730 ° C, and the film forming time was 20 minutes. The same operation as above was performed, but no inorganic film was obtained.

Items related to Examples 1 to 4 and Comparative Example 1 are shown below as a table. A coating material cannot be obtained at a laser power density of 28 W / cm ² and a film forming temperature of 730 ° C. However, a first coating in which a black BCN film is formed at a film forming temperature of 32 to 64 ^{W / cm 2 and a film forming temperature of 930 to 1150 ° C.} The material was obtained. Further, from Examples 1 to 3, it was found that the higher the laser power density and the film forming temperature, the higher the film forming speed.

5. Production and Evaluation of Second Covering Material (1) Example 5
Under the same conditions as in Example 1, a first coating material 10 having a black BCN coating 30 on the surface 20a of the base material 20 and serving as a precursor of the second coating material 40 was obtained. The obtained first coating material 10 was placed on a support base 69 of the film forming chamber 61, and an annealing treatment was performed by irradiating the surface with a laser.
In the annealing treatment, the inside of the film forming chamber 61 is made into an atmospheric atmosphere, the surface 30a of the BCN coating 30 of the first coating material 10 is irradiated with a laser, and the annealing treatment is performed at a surface temperature of 950 ° C. of the surface 30a of the BCN coating 30 for 5 minutes. went.
As a result, the upper part of the BCN coating 30 was changed to the BCNO coating 50, and the second coating material 40 was formed.

The second coating material 40 was black and emitted orange light under ultraviolet irradiation. FIG. 9 is a bright-field image obtained by observing a cross section near the surface of the BCNO coating 50 after the annealing treatment at 950 ° C. with a transmission electron microscope (manufactured by JEOL Ltd., the same applies hereinafter to the model “JEM2100F”).
As shown in FIG. 9, the surface morphology of the BCN coating 30 that was smooth in the first coating material 10 became the morphology of the BCNO coating 50 having irregularities of about 500 nm at the maximum by the annealing treatment, and the depth was 50 to 300 nm from the surface. An area with bright contrast was observed.

FIG. 10 is a high-resolution transmission electron microscope image and an electron diffraction image (lower left of FIG. 10) in a bright contrast region of the BCNO coating 50. In the BCNO coating 50, a striped layered structure having a layer spacing of 0.34 nm was observed, and this layered structure was formed substantially parallel to the surface 20a (the surface of the BCNO coating 50) of the base material 20. This layered structure corresponds to two strong and wide diffraction spots in the electron diffraction image. This indicates that the amorphous BCN coating 30 was changed to the BCNO coating 50 having a crystal structure having a hexagonal BN as a skeleton by the annealing treatment, and the orientation in which the C plane of the hexagonal BN skeleton structure was close to parallel to the substrate. It shows that it was formed in.
The composition of this BCNO coating 50 is analyzed by X-ray photoelectron spectroscopy (XPS, manufactured by ULVAC-PHI, Ltd.,
Analysis by model "VersaProbe PHI5000", source: monochromatic AlKα, 15 kV, 25 W, beam diameter: 100 μm), B _{0.48 to 0.41} C _{0.03 to 0.26} N _{0.24 to 0.25} The O was _0.09 to 0.26, and no other metal elements were detected. The composition of the XPS analysis has a range because there is a composition change in the depth direction from the surface by the depth analysis by Ar sputtering. For example, in order to remove impurities on the outermost surface, the composition after 1 minute of sputtering treatment with 3 kV Ar ions (spattering rate is 20 nm / min with respect to silica) is B _0.46 C _0.03 N _{0. 26} O _0.26 , the composition after 21 minutes of sputtering is B _0.45 C _0.12 N _0.25 O _0.19 , the composition after 31 minutes of sputtering is B _{0. It was 41} C _0.26 N _0.24 O _0.09 . The fluorescence characteristics of this black base material with an inorganic coating were measured with a spectrofluorometer (FP-6500, JASCO Corporation) to obtain the excitation / emission spectra shown in FIG.
As shown in FIG. 11, the excitation spectrum at an emission wavelength of 550 nm was observed at 300 to 450 nm (the spectrum on the left in FIG. 11). When excited at an excitation wavelength of ultraviolet light of 375 nm, it showed a wide emission spectrum of 450 to 650 nm, and the center wavelength was about 580 nm (spectrum on the right in FIG. 11).

(2) Example 6
Under the same conditions as in Example 1, a first coating material 10 having a black BCN coating 30 on the surface 20a of the base material 20 and serving as a precursor of the second coating material was obtained. The obtained first coating material 10 was subjected to an annealing treatment at 800 ° C. for 1 hour in an electric furnace (Siliconit furnace SC manufactured by Motoyama Co., Ltd.) to obtain a second coating material 40.
It is probable that the coating film of the second coating material 40 taken out from the electric furnace was black and partly translucent, and the BCN coating film 30 was almost changed to the BCNO coating film 50. The BCNO coating 50 of the second coating material 40 emitted yellow light under ultraviolet irradiation.
The fluorescence characteristics of this BCNO coating 50 were measured with a spectrofluorometer, and the excitation / emission spectra shown in FIG. 12 were obtained.
As shown in FIG. 12, the excitation spectrum at an emission wavelength of 545 nm was observed at 300 to 430 nm (the spectrum on the left in FIG. 12). When excited at an excitation wavelength of ultraviolet rays of 360 nm, it showed a slightly narrow emission spectrum of 500 to 600 nm, and the center wavelength was about 540 nm (spectrum on the right in FIG. 12).

(3) Example 7
Under the film forming conditions of Example 4, the same as in Example 4 except that the power density was 70 W / cm ² , the temperature of the substrate 20 surface 20a during film forming was 1150 ° C., and the film forming time was 11 minutes. The operation was carried out to obtain the first coating material 10 which is a precursor of the second coating material. Obtained-The obtained first coating material 10 was placed on a support 69 of a film forming chamber 61, and an annealing treatment was performed by irradiating the surface with a laser.
In the annealing treatment, when the inside of the membrane-forming chamber 61 was set to a reduced pressure atmosphere of 20 Pa or less, oxygen gas was supplied to the membrane-forming chamber 2 at a flow rate of 250 sccm (linear velocity of gas flow 2.36 cm / s), and the membrane-forming chamber 2 was subjected to. The inside of the film was set to 1000 Pa, irradiated with a laser, and annealed at a surface temperature of 986 to 1040 ° C. for 30 minutes. As a result, the upper part of the BCN coating 30 was changed to the BCNO coating 50, and the second coating material 40 was formed. The covering material 40 was black and showed yellow light emission under ultraviolet irradiation. As a result of measuring the fluorescence characteristics with a spectrofluorometer, as shown in FIG. 13, when excited at an excitation wavelength of ultraviolet rays of 400 nm, a slightly narrow emission spectrum of 500 to 650 nm was exhibited, and the center wavelength was about 560 nm. ..

(4) Example 8
Under the same conditions as in Example 1, a first coating material 10 having a black BCN coating 30 on the surface 20a of the base material 20 and serving as a precursor of the second coating material was obtained.
The obtained first coating material 10 was placed on a base material support 69 in the film forming chamber 61, and the surface of the BCN coating 30 of the first coating material 10 was irradiated with a laser to perform an annealing treatment. In the annealing treatment, when the inside of the film forming chamber 61 is set to a reduced pressure atmosphere of 20 Pa or less, oxygen gas is supplied to the film forming chamber 2 at a flow rate of 250 sccm (linear speed 2.36 cm / s), and the inside of the film forming chamber 2 is filled. It was set to 1000 Pa, irradiated with a laser, and annealed at a surface temperature of 1020 to 1050 ° C. for 30 minutes.
As a result, a second coating material 40 having a black BCNO coating 50 that emits orange light under ultraviolet irradiation was obtained.
As it is, the inside of the film forming chamber 61 was made into an atmospheric atmosphere, laser irradiation was performed, and annealing was performed at a surface temperature of the BCN film 50 at a surface temperature of 820 to 850 ° C. for 10 minutes. Material 40 was obtained. The fluorescence characteristics of the BCNO coating 50 of the second coating material 40 were measured by a spectrofluorometer, and the excitation and emission spectra shown in FIG. 14 were obtained. As shown in FIG. 14, the excitation spectrum at the emission wavelength of 580 nm was observed at 320 to 450 nm (the spectrum on the left in FIG. 14). When excited at the excitation wavelength of ultraviolet rays of 380 nm, it showed a wide emission spectrum of 500 to 700 nm, and the center wavelength was about 580 nm (spectrum on the right in FIG. 14).

The matters relating to Examples 5 to 8 are shown below as a table. In the annealing treatment, the second coating material 40 could be produced at 800 to 950 ° C. in the air and 986 to 1050 ° C. under reduced pressure (oxygen partial pressure 1000 Pa). In addition, the emission wavelength and emission color changed by changing the annealing temperature, time, and atmosphere.

No light emission was observed in the first coating material 10 having BCN obtained in Example 1 even when it was irradiated with ultraviolet rays in the same manner as in Examples 5 to 8. It was confirmed that the coating material did not fluoresce when the oxygen content was 1.6 atomic%.

Since the first coating material according to the present invention is a hard black coating material composed of light elements of boron, nitrogen, and carbon, it is a hard cutting tool with less environmental load and resource risk, and excellent wear resistance and design. It can be used for various optical parts, semiconductor parts, and jewelry. Since the second coating material is a fluorescent coating material composed of light elements such as boron, nitrogen, carbon, and oxygen, it can be applied to inorganic LEDs, light emitting elements, various optical parts, jewelry, and semiconductor parts.

10: First dressing,
20: Substrate, 20a; Surface,
30; BCN coating, 30a; surface,
40; 2nd dressing,
50; BCNO coating,
60; Manufacturing equipment,
61; Membrane formation room,
62: Decompression means,
63; Raw material gas supply means, 631; Mass flow controller,
64: Raw material gas adjusting means, 641, 642; storage tank, 643; heater,
65: Carrier gas supply means,
67; Laser Irradiation Means, 671; Light Diffusing Lens, 672; Window Material,
68; Temperature measuring instrument, 681; Window material,
69: Base material support.

Claims (9)

A first coating material comprising a base material and a BCN coating that covers at least a part of the surface of the base material, and does not emit fluorescence under ultraviolet irradiation. The first coating material according to claim 1, wherein the oxygen content of the BCN coating is less than 5 atomic%. A second coating material comprising a base material and a BCNO coating that covers at least a part of the surface of the base material, and fluoresces under ultraviolet irradiation. When the oxygen content on the outermost surface of the BCNO coating is 5 atomic% or more and B _x C _y N _z O _(1-x-y-z) , the B atomic molar ratio (x) is 0.2 to 0.2 to 0.7, C atomic molar ratio (y) is 0.01 to 0.6, N atomic molar ratio (z) is 0.1 to 0.6, O atomic molar ratio (1-x-yz) is The second coating material according to claim 3, which is 0.05 to 0.5. The third or fourth aspect of the present invention, wherein the BCNO film has a layered structure having a layer spacing of 0.5 nm or less in cross-sectional microstructure observation, and the surface of each layer is arranged parallel to the base material in a region of at least 10 nm or more. 2 Covering material. The second coating material according to any one of claims 3 to 5, wherein the BCNO coating has a fluorescence characteristic of an emission wavelength of 400 to 800 nm under irradiation with an excitation wavelength of 200 to 450 nm. The method for producing a first coating material according to claim 1 or 2, wherein a vaporized substance of an organic compound containing a boron atom is retained on the surface of the base material in a state where a gas containing an oxygen atom is not supplied. A method for producing a first coating material, which comprises irradiating the vaporized compound with a laser having a power density of 30 W / cm ^{2 or more.} The method for producing a second coating material according to any one of claims 3 to 6, wherein the first coating material according to claim 1 or 2 is in an atmosphere in which oxygen is present under atmospheric conditions or reduced pressure. A method for producing a second coating material, which is produced by an annealing treatment in the above. The method for producing a second coating material according to any one of claims 3 to 6, wherein a mixture of a vaporized product of an organic compound containing a boron atom and an oxidizing gas is retained on the surface of a base material. A method for producing a second coating material, which comprises irradiating the vaporized compound with a laser having a power density of 30 W / cm ^{2 or more in the state.}

Images