JPH0295900A - Accessary and production thereof - Google Patents

Abstract

PURPOSE:To obtain inexpensively an accessary having the feeling of a quality article by providing a crystal of diamond in the shape of a desired character or figure on a surface by vapor phase synthesis. CONSTITUTION:A surface of a substrate 1 capable of enduring a temperature at which a crystal of diamond is provided by vapor phase synthesis is provided with minute recesses and protrusions 2 by minutely scratching the surface by a diamond abrasive or the like. A desired character or figure is drawn on the surface by use of a masking agent 3 such as a coating material, a seal and a marker ink. Next, the surface of the substrate 1 is made flat by etching. In this case, it is necessary that the masking agent 3 is not removed completely. The masking agent 3 remaining on the surface after the etching is removed by an acid, an organic solvent or the like, and the substrate is cleaned with an organic solvent or the like. Then, a crystal of diamond is provided selectively on the unetched part of the surface of the substrate 1 by vapor phase synthesis. Thus, a crystal of diamond can be provided at a desired position on an inexpensive substrate to produce an accessary, whereby an accessary having an enhanced value as accessary and having the feeling of a quality article can be obtained inexpensively.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an ornament whose surface has diamond crystals formed by vapor phase synthesis, and a method for producing the same.

(Prior art) Diamonds have traditionally been used as gemstones, but recently a method of forming diamonds using a vapor phase synthesis method has become known. Publication No. 58-110494, Special Publication No. 61-2632
It is stated in the publication number etc.

It is also known to form this vapor-phase synthetic diamond on the surface of gemstones other than diamonds, such as emeralds and rubies, and use it as a protective film for the gemstones (Japanese Patent Laid-Open No. 61-3619).
9).

Further, Japanese Patent Laid-Open No. 62-297298 discloses a selective deposition film forming method for selectively forming diamonds at desired positions.

(Problem to be Solved by the Invention) However, none of these conventional examples have been applied to the decoration of decorative items, and even if it is attempted to decorate the desired shape at the desired position of the decorative item, it is difficult to apply it. was there.

The present invention has been made in view of the above-mentioned points, and its purpose is to provide a novel and useful ornament that has not been seen in the prior art, and a method for producing the same.

[Means to solve the problem]

The decorative article of the present invention which achieves the above object is characterized in that diamond crystals are provided on the surface in the shape of desired letters or figures by vapor phase synthesis.

Further, the method for forming a decorative article of the present invention that achieves the above object is as follows:
It is characterized by selectively providing diamond crystals in the shape of desired characters or figures on the surface of decorations and ornaments by vapor phase synthesis.

[Effect]

According to the present invention constructed in this way, by forming diamond crystals in the shape of a desired character on the surface of an ornament, the value as an ornament can be further increased, and the value of the ornament can be further increased. It is possible to provide decorative items with a sense of style at a low cost.

In addition, by configuring the area where diamond crystals are provided with fine dots or lines and selectively forming diamond crystals on the area, it exhibits beautiful interference colors due to light diffraction, making it extremely beautiful and excellent as an ornament. can be obtained.

The present invention will be specifically explained below with reference to FIG.

FIG. 1 is a schematic process diagram for explaining one of the preferred embodiments of the present invention for forming diamond crystals on a desired substrate constituting an ornament.

"Step (A)" First, a substrate 1 (made of quartz, alumina, silicon, tungsten, tantalum, etc.) that can withstand the temperature during diamond crystal formation by vapor phase synthesis is prepared.

"Step (B)" Fine scratches are formed on the surface of the substrate 1 using diamond abrasive grains or the like to provide fine irregularities 2. These minute scratches serve as starting points for the generation of nuclei that grow into diamond crystals.

"Process (C)" Paint and seal on the substrate 1 on which minute scratches have been formed.

Then, using a masking agent 3 such as marker ink, a desired character 1 figure is drawn.

"Step (D)" The surface of the substrate 1 to which the treatments up to step (C) have been applied is etched to a depth of about 1 to 0.05 μm to flatten it. In this etched area, step (B)
The scratches formed by this process are removed and the surface is flattened, so no nuclei that grow into diamond crystals are generated. Any etching method may be used here, but it is necessary that the masking agent 3 provided on the surface of the substrate 1 in step (C) is not completely removed by the etching. As a specific etching method, if the substrate is quartz, hydrofluoric acid can be used, and if the substrate is metal, hydrochloric acid, sulfuric acid, etc. can be used. In addition, ion sputter etching equipment (
For example, it is also possible to perform etching using JEOL JFC-1100) or the like.

``Step (E)J: After removing the masking agent 3 remaining on the substrate 1 using an acid, an organic solvent, etc., cleaning is performed using an organic solvent, etc. At this time, the cleaning method may be insufficient and uneven cleaning may occur. If there is, diamond crystals will tend to precipitate in undesired locations, so care must be taken.

"Step (F)" Next, the substrate 1 is subjected to, for example, a hot filament CVD method using an apparatus as shown in FIG. 2, a microwave plasma CVD method using an apparatus as shown in FIG. Using a known vapor phase synthesis method, diamond crystals are selectively formed in the areas that were not etched in step (C).

In this way, diamond crystals can be formed at desired positions on inexpensive substrates to produce decorative items. Furthermore, by adding processing such as attaching an outer frame or chain to the decorated base as described above, or fitting the decorated base as described above into a desired workpiece, it can be shaped into a desired shape. It can be used as a badge, pendant, ornament, tie clip, ring, eyeglass frame, earring, lighter, watch, or other high-class ornaments provided with diamond crystals.

Next, an example in which diamond crystals are provided in a desired shape by the method of the present invention on the surface of a substrate having a desired shape using the apparatus shown in FIGS. 2 and 3 will be briefly described.

When using the hot filament CVD apparatus shown in Fig. 2, the first
The substrate 8 that has undergone steps (A) to (E) in the figure is placed in a reaction tube 5.
The inside of the reaction tube 5 is evacuated from the exhaust port 10 to reduce the pressure to a desired pressure. Methane from the gas introduction pipe,
A raw material gas such as ethane is introduced and the inside of the reaction tube 5 is brought to a desired temperature using an electric furnace 6, and then electricity is applied to a tungsten hot filament 8 to form diamond crystals in a desired shape on the substrate 8.

When using the microwave plasma CVD apparatus shown in Fig. 3;
The substrate 15 that has undergone steps (A) to (E) in FIG. 1 is placed on the substrate holder 16 inside the reaction tube 11, and the inside of the reaction tube 11 is evacuated from the exhaust port 18 to reduce the pressure to a desired pressure. Next, raw material gas is introduced through the gas introduction pipe 17. A plunger 14 is used to generate microwaves with a magnetron 12 and guide them into the reaction tube 11 through a waveguide 13 to obtain a standing wave.
is adjusted to form diamond crystals in a desired shape on the substrate 15.

Next, the present invention, in which the area where diamond crystals are provided is formed of fine dots or lines, will be explained in detail with reference to FIG. 4.

FIG. 4 is a schematic process diagram for explaining one of the preferred embodiments of the present invention.6 "Step (A)" First, a substrate that can withstand the temperature during diamond crystal formation by vapor phase synthesis method is prepared. ! 9 (quartz and alumina.

(silicon, tungsten, tantalum, etc.).

"Step (B)" Fine scratches are formed on the surface of the base 19 using diamond abrasive grains or the like to provide fine irregularities 20. These minute scratches serve as starting points for the generation of nuclei that grow into diamond crystals.

"Step (C)" A desired character 1 figure is drawn in the form of fine dots or lines on the substrate 19 in which minute scratches have been formed by disposing a resist 21 such as PMMA. A method for forming the resist 21 includes a method of applying the resist to the entire surface of the substrate 20 and forming it into dots or lines by a method such as photolithography. At this time, in order for the diamond crystal to exhibit beautiful interference colors, dots or lines should be
Preferably 200μm pitch, more preferably 100μm
It is desirable to form them at a pitch of m, most preferably a pitch of 20 μm or less.

Further, the dot diameter or line width is preferably 100 μm or less or 100 μm or less, more preferably 50 μm or less or 50 μm or less.

"Step (D)" The surface of the substrate 19 to which the treatments up to step (C) have been applied is etched to a depth of about 1 to 0.05 μm to flatten it. In this etched area, the process (B
) is removed and the surface is flattened, so no nuclei that grow into diamond crystals are generated. Any etching method may be used here, but
It is necessary that the resist 21 provided on the surface of the substrate 19 in step (C) is not completely removed by the etching.

The above etching may be either dry etching or wet etching. When performing wet etching, for example, etching with a mixed solution of hydrofluoric acid and nitric acid can be used. Further, when dry etching is performed, for example, plasma etching, ion beam etching, etc. can be used.

"Step (E)" The resist 21 remaining on the substrate 19 is removed using an organic solvent or a mixed solution of sulfuric acid and hydrogen peroxide, and the substrate is also cleaned.

"Step (F)" Diamond crystals 22 are selectively formed on the surface of the substrate 19 by vapor phase synthesis in areas that were not etched by applying the resist 21. At this time, since the diamond crystals are formed in the form of fine dots or lines, they exhibit beautiful colors with interference colors, making them very beautiful and excellent ornaments.

The vapor phase synthesis method used in the present invention is not limited to the above-mentioned thermal filament CVD method and microwave plasma CVD method, but includes RF plasma CVD method, ECR plasma CVD method, and electron beam assisted CVD method (EACVD method). Any gas phase synthesis method such as 2) may be used. Further, as the raw material gas, a mixed gas of hydrogen and methane is usually used, but in order to improve the deposition rate, an organic solvent such as alcohol or acetone may be introduced by bubbling hydrogen gas. Further, it can be used as a carbon source such as halogenated carbon or CO gas, and it is also effective to introduce 02 gas or H20 gas as an additive gas to improve crystallinity.

〔Example〕

<Example 1> The badge shown in Figure 5 was created as follows.

A Si substrate 23 (φ25 mm, thickness O', 5 mm) is placed in an ultrasonic cleaner with an alcohol solution in which diamond abrasive grains (particle size ~20 μm) are dispersed, and ultrasonic treatment is performed for 60 minutes to clean the surface of the substrate 23. microscopic scratches were formed on the surface. Next, a "heart" picture was drawn on the surface of the base 23 with marker ink. Subsequently, the surface of the substrate 23 is etched by an ion sputter etching device (JFC-1100 manufactured by JEOL Ltd.) for about 50 minutes.
I etched 00 people. At this time, the pictures drawn with magic ink remained. This substrate 23 is ultrasonically cleaned with an acetone solution for 10 minutes to remove the ink and clean the substrate 23. Then, diamond crystals are formed on the substrate 23 using the hot filament CVD apparatus shown in FIG. 2 under the following formation conditions. was formed.

(Formation conditions) H2 gas flow rate: 200SCCM CH4 gas flow rate: I SCCM pressure ・
50Torr Substrate temperature ・820℃ After 4 hours of film formation, heart-shaped polycrystalline diamond crystal 2
4 was formed.

This board was used for badges by painting the outer frame.

<Example 2> After performing the same ultrasonic treatment as in Example 1 on a quartz substrate (φ20 mm, thickness 1 mm), a resist (manufactured by Tokyo Ohka Co., Ltd., O
MR) wrote ``r'I Love You''.

The surface of this substrate was etched with a hydrofluoric acid solution (concentration 5%) by about 500 people. After removing the resist and cleaning this substrate with an acetone solution, diamond was formed using the same apparatus and forming conditions as in Example 1.
Diamond crystals were precipitated in the shape of "You". This base was used as a pendant by fitting an outer frame.

<Example 3> After performing the same ultrasonic treatment as in Example 1 on a Si substrate (10 x 25 mm, thickness 1.5 mm), rJAPAN was applied on the surface of the Si substrate using a resist (manufactured by Tokyo Ohka, OMR).
I wrote J.

After performing the same etching treatment as in Example 1 on the surface of this substrate, the resist was removed and washed with an acetone solution for 10 minutes, and diamond formation was performed using the microwave plasma CVD apparatus shown in FIG. 3 under the following formation conditions. .

(Formation conditions) (CHs)2 Co and H2 mixed gas flow i: 200SCCM pressure
60Torr Substrate temperature ・850℃ Microwave power, 450W (Acetone was introduced by bubbling with hydrogen gas, acetone concentration 1%
) After 3 hours of film formation, diamond crystals were formed in the shape of rJAPANJ, and this substrate was used as a tie clip by attaching an outer frame and a pin.

<Example 4> After a Si substrate (10 x 25 mm, thickness 1.5 mm) was subjected to the same ultrasonic treatment as in Example 1, a resist (0EBR-1000 manufactured by Tokyo Ohka Co., Ltd.) was applied to the surface of the substrate using a spinner.
) and apply mask aligner (Canon; PLA-).
500) to form a resist pattern with a diameter of 5 μm.
rU, S, A at 1.5mm in the letter in a lattice shape with a μm pitch
, J shape (size of approximately 8 x 24 mm).

Diamond crystal formation was performed on this substrate under the same etching and formation conditions as in Example 3.

Due to this diamond crystal formation, diamond crystals were formed in the form of fine dots rU, S, A, and J, so the diamond crystal forming area exhibited a beautiful color with interference color. It was also made into a tie pin.

<Example 5> A resist pattern was formed in a line shape with a width of 10 μm at intervals of 10 μm. Diamond crystals were formed under the same conditions as in Example 4 except for these conditions. Depending on this diamond crystal formation, fine lines rU, S, A,
Because the diamond was formed in the form of , the diamond-formed part exhibited a beautiful color with interference color due to light diffraction, and was processed into a tie pin in the same manner as in Example 3.

(Effects of the Invention) According to the present invention, by forming diamond crystals in the shape of a desired character on the surface of an ornament, the value as an ornament can be further increased, and the ornament has a high-class feel. can be provided at low cost. In addition, by configuring the area where diamond crystals are provided with fine dots or lines and selectively forming diamond crystals on the area, it exhibits beautiful interference colors due to light diffraction, making it extremely unique and excellent as an ornament. can get things.

[Brief explanation of drawings]

Fig. 1 is a process diagram schematically representing one example of the method for forming diamond crystals according to the present invention, Fig. 2 is a schematic configuration diagram of a thermal filament CVD apparatus, and Fig. 3 is a schematic diagram of a microwave PCVD apparatus. Fig. 4 is a process diagram schematically representing one preferred example of a method for forming diamond crystals in which the diamond forming region is formed into a fine dot shape or a line shape according to the present invention; 1 is a schematic configuration diagram of a badge created in Example 1. FIG. l...Base 2...Base with minute scratches 3...Masking agent such as ink, paint, etc. 4...Diamond crystal 5...Reaction tube 6...Electric furnace 7...Made of tungsten Thermal filament 8...Base 9...Gas inlet 0...Exhaust port 1...Reaction tube 2...Magnetron 3...Waveguide 14...Plunger body 15...Substrate 16...Substrate holder 17...Gas inlet 18...Exhaust port 19...Substrate 20...Substrate 21 with minute scratches...Resist capacitor; 22...Diamond crystal 23...Si substrate 24...Diamond crystal film

Claims (3)

[Claims] (1) An ornament characterized in that diamond crystals are provided on the surface in the shape of desired letters or figures by a vapor phase synthesis method. (2) The ornament according to claim 1, wherein the diamond crystal is formed in a dot shape or a line shape. (3) A method for producing an ornament, which comprises selectively providing diamond crystals in the shape of desired letters or figures on the surface of the ornament by vapor phase synthesis.