WO2023035287A1 - Ornement revêtu d'un film de diamant et procédé de préparation de revêtement de film de diamant - Google Patents

Ornement revêtu d'un film de diamant et procédé de préparation de revêtement de film de diamant Download PDF

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WO2023035287A1
WO2023035287A1 PCT/CN2021/118355 CN2021118355W WO2023035287A1 WO 2023035287 A1 WO2023035287 A1 WO 2023035287A1 CN 2021118355 W CN2021118355 W CN 2021118355W WO 2023035287 A1 WO2023035287 A1 WO 2023035287A1
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moissanite
diamond
diamond film
jewelry
conformal
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PCT/CN2021/118355
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Chinese (zh)
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吕反修
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吕反修
何金鑫
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    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C17/00—Gems or the like
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/503—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using dc or ac discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges

Definitions

  • the invention relates to a diamond film coating ornament and a method for preparing the diamond film coating, belonging to the field of chemical coating.
  • Moissanite is a single crystal form of silicon carbide (SiC), which does not exist naturally in the Earth's environment (Moissanite is found in craters and is believed to come from extraterrestrial bodies).
  • Synthetic moissanite is an excellent wide-bandgap semiconductor material, and it is one of the main research objects of a new generation of high-performance semiconductor materials around the world.
  • the refractive index of moissanite is 2.46-2.59, which is higher than that of diamond (diamond) (2.42), so its brilliance (fire color) is better than that of diamond.
  • its thermal conductivity is also very high (490W/cm.K), so it is a high imitation diamond with the highest fidelity with diamond (diamond).
  • Moissanite is also very hard (Mohs hardness 9.2), it is still significantly different from diamond hardness (Mohs hardness 10). Therefore, a layer of diamond film (diamond) film is applied on the surface of Moissanite jewelry, so that it has the same physical and chemical properties as diamonds, but also has the same high hardness as diamonds, and it will never wear and tear like diamonds. "Grains will last forever” has become the goal pursued by people.
  • Neogi et al disclosed in US Patent (US20160029748A1) a method for preparing a nano-diamond coating on the surface of various gem ornaments including Moissanite by using a nano-diamond powder slurry dip coating method.
  • the slurry dipping method is essentially a physical method.
  • the adhesion between the nano-diamond coating and the gemstone substrate only comes from the "Van der Waals force" between the nano-diamond particles and the gemstone surface atoms, which is a weak force. force, thus resulting in poor adhesion.
  • K. Nassau et al once disclosed in the patent (CN108823550A, WO98/21386) a method of applying a diamond film coating on the surface of moissanite (Moissanite) ornaments by chemical vapor deposition (CVD). Due to the special shape of gem ornaments (such as diamond rings), K. Nassau and others designed a sample table with a round hole, so that the diameter of the round hole is slightly smaller than the girdle diameter of the diamond ring ornaments.
  • the pavilion of the pointed (inverted cone) can be placed firmly in the round hole, and the table and crown of the diamond ring are placed in the diamond film deposition atmosphere (H 2 /CH 4 , or H 2 / CH 4 /Ar high temperature or high temperature plasma atmosphere) to achieve the purpose of depositing diamond film.
  • the diamond film deposition atmosphere H 2 /CH 4 , or H 2 / CH 4 /Ar high temperature or high temperature plasma atmosphere
  • the pavilion of the diamond ring jewelry is in the shape of an inverted pyramid, there are only a few edges of the pavilion in contact with the circular hole, and they are all point contacts, which will inevitably lead to a high temperature (or high temperature plasma) atmosphere for diamond film deposition.
  • the heat conduction between the moissanite sample in the sample and the sample stage becomes extremely poor (thermal blockage).
  • the Moissanite sample will inevitably heat up rapidly until it is higher than the optimum temperature range (700-1000°C) required for diamond film deposition.
  • the present invention aims at the defect that the above-mentioned circular hole sample stage cannot effectively dissipate heat, and proposes an improved sample stage design, which changes the thermal contact between the moissanite and the sample stage from point contact to surface contact, so that it can High optical quality diamond film-coated moissanite ornaments were prepared under conditions within a range of quality diamond film deposition process parameters.
  • the present invention also proposes a surface pretreatment method that can greatly increase the nucleation rate of the diamond film on the moissanite surface, aiming at the requirement of extremely low surface roughness of the optical coating. At the same time, the preparation process of diamond film-coated moissanite jewelry was optimized.
  • the object of the present invention is to provide a diamond film coated ornament.
  • Another object of the present invention is to provide a method for preparing a diamond film coating on the surface of an ornament.
  • a diamond film-coated ornament is characterized in that a layer of diamond film coating is coated on the surface of the moissanite ornament, the average grain size of the diamond film is 50 nanometers to 200 nanometers, the surface roughness is less than 10nm, and the thickness of the diamond film is 0.1-200 nanometers. 0.5 microns.
  • the diamond film-coated ornament is prepared through the following steps:
  • Ultrasonic grinding pretreatment is carried out to moissanite jewelry in the suspension of nano-diamond powder; The time is 1 hour ⁇ 6 hours;
  • diamond film deposition adopts "two-stage method": nucleation stage and growth stage, the concentration of methane in the nucleation stage is 3% ⁇ 10%, and the time is 5 ⁇ 20 minutes; The methane concentration in the growth stage is 0.5% ⁇ 2%, and the time is 10 minutes ⁇ 120 minutes; the pressure of the deposition furnace is set at 3kPa ⁇ 20kPa.
  • the plasma treatment and the in-situ diamond film deposition adopt DC arc plasma jet CVD or microwave plasma CVD.
  • the moissanite jewelry adopts nano-diamond suspension for ultrasonic grinding pretreatment; the diamond particle size in the nano-diamond suspension is between 5 nanometers and 200 nanometers, and the concentration of the nano-diamond particles is 5%-20%. Grinding pretreatment time is 1 hour ⁇ 6 hours.
  • the pure copper conformal sample stage has an inverted conical conformal hole, and its cone angle is slightly smaller than that of the inverted pyramid at the moissanite jewelry pavilion, with a deviation of 0° ⁇ -2°, and a certain force will be applied during use.
  • the moissanite jewelry is pressed into the inverted conical conformal hole of the conformal sample stand, forcing the conical hole to undergo plastic deformation, forming surface contact with the edges and corners of the moissanite jewelry pavilion placed on it.
  • the diamond film-coated ornament described in this application is prepared through the following steps:
  • Ultrasonic grinding pretreatment is carried out to moissanite jewelry in the suspension of nano-diamond powder; The time is 1 hour ⁇ 6 hours;
  • diamond film deposition adopts "two-stage method": nucleation stage and growth stage, the concentration of methane in the nucleation stage is 3% ⁇ 10%, and the time is 5 ⁇ 20 minutes; The methane concentration in the growth stage is 0.5% ⁇ 2%, and the time is 10 minutes ⁇ 120 minutes; the pressure of the deposition furnace is set at 3kPa ⁇ 20kPa.
  • the plasma treatment and the in-situ diamond film deposition adopt DC arc plasma jet CVD or microwave plasma CVD.
  • the moissanite jewelry adopts nano-diamond suspension for ultrasonic grinding pretreatment; the diamond particle size in the nano-diamond suspension is between 5 nanometers and 200 nanometers, and the concentration of the nano-diamond particles is 5%-20%. Grinding pretreatment time is 1 hour ⁇ 6 hours.
  • the pure copper conformal sample stage has an inverted conical conformal hole, and its cone angle is slightly smaller than that of the inverted pyramid at the moissanite jewelry pavilion, with a deviation of 0° ⁇ -2°, and a certain force will be applied during use.
  • the moissanite jewelry is pressed into the inverted conical conformal hole of the conformal sample stand, forcing the conical hole to undergo plastic deformation, forming surface contact with the edges and corners of the moissanite jewelry pavilion placed on it.
  • An improved conformal hole sample stage It can be used to prepare diamond film-coated moissanite ornaments with high optical quality.
  • the conformal sample stage should be made of materials with high thermal conductivity, easy deformation, and resistance to high temperature and atomic hydrogen etching in the diamond film deposition environment. Pure copper is the best choice. Although molybdenum and tungsten have good thermal conductivity, they are difficult to undergo plastic deformation.
  • Graphite has good thermal conductivity and plastic deformation ability, but it is very easy to be etched by atomic hydrogen, so it is not recommended to use .
  • the conformal inverted cone sample stage made of pure copper can greatly improve the heat conduction ability from the diamond ring sample through the sample stage during the diamond film deposition process, so that it can be processed under conditions close to high optical quality diamond film deposition (high power, high pressure , close distance (from the excitation source)) to deposit high optical quality diamond film coating on the surface of the diamond ring jewelry (table and crown). This is further illustrated in Figure 2.
  • the present invention adopts a method for ultrasonically grinding and pretreating moissanite ornaments in a suspension of nano-diamond powder to achieve the purpose of uniform nucleation of ultra-high-density diamonds.
  • ultra-high-density diamond nucleation is achieved by ultrasonic grinding of nano-diamond suspensions
  • most of the substrate materials used are single crystal silicon or silicon oxide (OAWilliams et al.Diamond & Related Materials 15 (2006) 654 –658)
  • the diamond nucleation density can reach 10 10 -10 12 /cm 2 .
  • the present invention utilizes nano-diamond suspension to carry out ultrasonic pretreatment on moissanite ornaments to realize ultra-high density diamond nucleation, so far there is no literature report.
  • the diamond nucleation density is as high as 2.5x10 13 /cm 2 . It strongly guarantees the diamond film coating with extremely low surface roughness.
  • the surface roughness of the diamond film coating finally obtained by the present invention is less than Ra 10nm.
  • An example of ultra-high-density uniform nucleation of a diamond film is shown in Figure 3.
  • a method for coating a diamond film on the surface of a moissanite ornament comprising the following steps: step 1: carrying out ultrasonic grinding pretreatment to the moissanite ornament in a suspension of nano-diamond powder; step 2: removing the moissanite ornament from The nano-diamond powder suspension is taken out, followed by ultrasonic cleaning with deionized water and absolute ethanol (alcohol); step 3: pressing the moissanite jewelry into the inverted tapered hole of the pre-selected conformal sample stage ; Step 4: placing the moissanite jewelry together with the conformal sample stage in a diamond film deposition furnace for plasma treatment; Step 5: injecting methane for in-situ diamond film deposition.
  • the nano-diamond particle size in the nano-diamond powder suspension is between 5 nm and 200 nm, and the concentration of the nano-diamond powder is 5% ⁇ 20%.
  • the time for the ultrasonic grinding pretreatment in the nano-diamond suspension is 1 hour ⁇ 6 hours.
  • step 3 the material of the conformal sample stage is pure copper.
  • the conformal sample stage is provided with an inverted conical hole for placing moissanite ornaments, and its cone angle is slightly smaller than the cone angle of the moissanite ornament pavilion (deviation is 0° to -2°).
  • a pressure of 50Kgf ⁇ 250Kgf (depending on the size of the moissanite ornament) is used to press the moissanite ornament into the inverted tapered hole of the conformal sample holder.
  • step 4 the plasma treatment adopts DC arc plasma injection or microwave plasma.
  • the temperature of the plasma treatment is 700°C-1000°C
  • the time of the plasma treatment is 5 minutes-30 minutes.
  • the purpose of plasma treatment is to completely remove the remaining organic root groups (derived from nano-diamond suspension) on the surface of moissanite jewelry, and activate the surface of moissanite jewelry.
  • the in-situ deposition of the diamond film in step 5 includes the following two stages: nucleation and growth of the diamond film.
  • concentration of methane in the nucleation stage is 3%-10%, and the time is 5-20 minutes; the methane concentration in the growth stage is 0.5%-2%, and the time is 10 minutes-120 minutes.
  • the pressure of the deposition furnace is set at 3kPa-20kPa.
  • the moissanite ornaments coated with diamond film on the surface prepared by the method of the present invention can show various physical and chemical properties of diamond while maintaining the optical properties (fire color) of moissanite, and its surface hardness reaches the hardness of diamond. It can greatly improve the scratch resistance of moissanite.
  • An improved method for preparing high optical quality diamond film coating on the surface of moissanite jewelry The prepared diamond film coated moissanite jewelry has the hardness and excellent hardness of diamond while maintaining the fire color of moissanite. scratch resistance performance.
  • the moissanite jewelry pavilion forms a surface contact, making it possible to deposit a high optical quality diamond film on the surface of the moissanite jewelry.
  • a method for realizing ultra-high density diamond nucleation on the surface of moissanite jewelry Ultrasonic grinding in nano-diamond suspension, combined with an optimized nucleation process, enables the diamond nucleation density to reach 2.5x10 13 /cm 2 .
  • a method for preparing a high-optical-quality diamond film on the surface of a moissanite ornament comprising the following steps: Step 1: Ultrasonic grinding pretreatment of the Moissanite ornament in a nano-diamond suspension; Step 2: Moissanite The ornaments are taken out from the nano-diamond powder suspension and cleaned; step 3: pressing the moissanite ornaments into the pre-set conformal sample stage so that it forms surface contact with the inverted tapered hole of the sample stage; step 4 : Place the moissanite jewelry together with the conformal sample stage in a diamond film deposition furnace for plasma treatment; step 5: feed methane, and use a two-stage method (nucleation stage and growth stage) to carry out the in-situ diamond film deposition.
  • the moissanite ornament coated with a diamond film on the surface of the present invention can maintain the optical performance (fire color) of the moissanite ornament while having various physical and chemical properties of diamond, and the surface hardness has reached the hardness of diamond, and has excellent Anti-scratch properties.
  • batch deposition of diamond film-coated moissanite ornaments can be realized.
  • the prepared diamond film-coated moissanite jewelry has the same fire color as the uncoated moissanite jewelry, and also has the hardness of diamond and excellent scratch resistance. It is a high-performance high imitation diamond product .
  • the preparation method described in the application can effectively overcome the poor thermal contact of the special-shaped moissanite (such as diamond ring) jewelry with the sample stage during the diamond film deposition process, it is difficult to obtain high quality, high light transmittance diamond film coating, and a large number of The temperature and the uniformity of the chemical vapor environment during the simultaneous deposition of samples are difficult.
  • the industrialized production of diamond film-coated Moissanite can be realized.
  • Figure 1 uses DC arc plasma jet diamond film CVD equipment, and the diamond-coated Moissanite jewelry prepared with a round-hole copper sample stage (see Figure 2 on the right) cannot obtain high optical quality diamond film coatings.
  • Left 6.5mm (1 carat) D color Moissanite uncoated sample (rough stone);
  • Middle The distance between the sample stage and the nozzle of the plasma torch is 60mm, the pressure is 2.3KPa (17Torr), the methane concentration is 1%, the input power 8KW.
  • the surface temperature of the Moissanite sample was as high as 1150°C, and the surface of the sample was completely blackened after only 10 minutes of deposition;
  • Right High-quality optical-grade F60mm self-supporting diamond film (unpolished) grown on the same equipment.
  • Process conditions nozzle distance 20mm, input power 20KW, pressure 6KPa (45Torr), methane concentration 0.5%, temperature 900°C, time 24 hours;
  • FIG. 2 Conformal pure copper sample stage with inverted conical hole. Left: Hole design for an inverted conical hole. The taper angle is 96°, the tolerance is 0o ⁇ -2o, the diameter of the taper hole is slightly smaller than the girdle diameter of the diamond ring to be coated, and a small-diameter round hole is designed in the lower part to prevent the tip of the diamond ring pavilion from breaking when it is pressed in. Before the diamond film is deposited, the moissanite jewelry to be coated is pressed into the conformal hole, forcing the plastic deformation of the contact part between the conformal hole and the inverted cone-shaped pavilion of the moissanite jewelry, thereby forming a surface contact.
  • Fig. 3 Field emission scanning electron micrograph of ultra-high density diamond nucleation.
  • Nucleation pretreatment Sonication in 30nm nanodiamond suspension for 2 hours.
  • Nucleation process DC arc plasma CVD system is adopted, the nozzle distance is 25mm, the pressure is 6KPa, the power is 10KW, the methane concentration is 4%, and the nucleation time is 10 minutes.
  • the size of the diamond crystal nucleus shown in the figure is only 15-20nm, and the diamond nucleation density is as high as 2.5x10 13 /cm 2 ;
  • FIG. 4 Comparison of fire color between diamond film coated Moissanite and uncoated (raw stone). Left: Uncoated, Right: Coated. A DC arc plasma jet CVD system is used. Coating process: nucleation: nozzle distance 25mm, pressure 6KPa, power 10KW, methane concentration 4%, nucleation time 10 minutes; growth: methane concentration reduced to 1%, time: 30 minutes;
  • Figure 5 Field emission scanning electron microscope (FSEM) image of the diamond film-coated Moissanite surface topography shown in Figure 4. It can be seen that the continuous dense diamond film shows obvious diamond (111) micro-facet characteristics, the average grain size is about 80-100nm, and the surface roughness is less than 10nm;
  • FSEM Field emission scanning electron microscope
  • Figure 7 left the surface morphology of diamond film-coated moissanite prepared by ultrasonic grinding of 5 micron and 1 micron mixed diamond powder for 2 hours pretreatment nucleation method and two-stage method (nucleation and growth). Discrete large-sized grains appear, and the fire color of the coated Moissanite becomes poor;
  • the Vickers hardness calculated according to the indentation measurement data shown in the figure is as high as 117GPa, the average hardness calculated according to 10 test points is 84 ⁇ 7GPa, and the diamond hardness is 80-110GPa.
  • the diamond film coating moissanite prepared by the technology of the present invention has reached the hardness of diamond;
  • Figure 9 Scratch resistance of diamond film-coated Moissanite.
  • the scratch tester is used for testing, single crystal diamond stylus, the maximum scribing pressure is 20N, the scribing distance is 2mm, and the acoustic emission signal is recorded while scratching.
  • the optical microscope image shows that the scribe needle has been carved into the moissanite, forming obvious grooves, showing many discontinuous lateral cracks on both sides of the grooves, corresponding to a series of discontinuous acoustic emission peaks on the acoustic emission spectrum.
  • FIG. 10 Thickness of diamond film coating.
  • the thickness of the diamond film coating was measured under a field emission scanning electron microscope using a prefabricated fractured mosaic sample. The thickness of the diamond film coating measured from the fracture image shown in the figure is 0.2-0.3 ⁇ m;
  • Fig. 11 adopts the 6.5mm (1 carat) diamond film-coated Moissanite drill produced in batches by the technology of the present invention.
  • the diameter of the sample stage is 62mm, which can allow 55 grains of 6.5mm (1 carat) diamond film-coated Moissanite to be deposited at one time;
  • Figure 12 is a comparison of fire color of diamond film-coated Moissanite and uncoated sample (raw stone) prepared by microwave plasma CVD system. Center position: Uncoated rough, left and right diamond coated samples. Adopt 6KW domestic microwave plasma CVD system. Power: 3KW; Pressure: 4.04KPa; Methane concentration: 5%; Plasma etching time: 5 minutes; Deposition time: 1.5 hours; The pretreatment process is the same as DC arc plasma CVD.
  • the most important core content of the present invention is the fundamental improvement of the circular hole sample stage that K. Nassau et al adopt in its disclosed patent technology.
  • the surface temperature of the Moissanite sample was as high as 1150°C, and the surface of the sample was completely blackened after only 10 minutes of deposition; right: a high-quality optical-grade ⁇ 60mm self-supporting diamond film (unpolished) grown on the same equipment.
  • Process conditions nozzle distance 20mm, input power 20KW, pressure 6KPa (45Torr), methane concentration 0.5%, temperature 900°C, time 24 hours. It can be seen from accompanying drawing 1 that the circular hole sample stage designed by K. Nassau et al. can only deposit diamond film under normal deposition conditions (low power, low pressure, long distance). Even so, the quality of the diamond film is too poor to meet the requirements for high optical quality diamond film coatings.
  • the present invention has designed a kind of inverted conical hole conformal pure copper sample stage.
  • Left Schematic diagram of the hole shape design for an inverted conical hole.
  • the taper angle is 96°
  • the tolerance is 0° to -2°
  • the diameter of the taper hole is slightly smaller than the girdle diameter of the diamond ring to be coated
  • a small-diameter round hole is designed in the lower part to prevent the tip of the diamond ring from breaking when it is pressed in.
  • the moissanite jewelry to be coated Before the deposition of the diamond film, the moissanite jewelry to be coated is pressed into the conformal hole, forcing the plastic deformation of the contact part between the conformal hole and the inverted cone-shaped pavilion of the moissanite jewelry, thereby forming a surface contact.
  • Another core content of the present invention is to realize ultra-high density (more than 10 10 /cm 2 ) diamond nucleation technology on the surface of Moissanite samples.
  • the optical properties of diamond film coatings depend on the intrinsic optical quality of the coating (i.e., the absorption coefficient, related to crystal structure and crystal defects) and the surface roughness of the diamond film (directly related to surface scattering). For optical coatings with very small thicknesses, the influence of surface roughness on optical properties is more important than that of crystal intrinsic quality.
  • the present invention adopts a nucleation pretreatment method of ultrasonic grinding in nano-diamond suspension to greatly increase the diamond nucleation density.
  • the diamond nucleation density is as high as 2.5x10 13 /cm 2
  • the specific process conditions are: the particle size of nano-diamond is 30 nm, and the ultrasonic treatment time is 2 hours: DC arc plasma CVD system is used , nozzle distance 25mm, pressure 6KPa, power 10KW, methane concentration 4%, nucleation time 10 minutes.
  • Another core content of the present invention is to form an optimized method for applying high optical quality diamond film coating on Moissanite. Its specific content is as follows:
  • the method includes the following steps: Step 1: performing ultrasonic grinding pretreatment on moissanite jewelry in nanometer diamond powder suspension.
  • the particle size of the nano-diamond powder is between 5 nanometers and 200 nanometers
  • the concentration of the nano-diamond powder is 5% ⁇ 20%
  • the pretreatment time of ultrasonic grinding is 2 hours ⁇ 6 hours.
  • the purpose of this step is mainly to increase the nucleation density of the diamond film deposition, so that the nucleation density of the diamond film is greater than 10 10 cm -2 .
  • step 2 take out the moissanite jewelry from the nano-diamond powder suspension, and clean it, and use deionized water and absolute ethanol (alcohol) to ultrasonically clean it according to the cleaning procedure. blow dry.
  • step 3 the moissanite jewelry is pressed into a preset conformal sample stage for maintenance.
  • Moissanite in order to keep Moissanite, with reference to Figure 2, an inverted conical hole for maintaining a Moissanite jewelry can be provided in the conformal sample stand, and the depth of the conical hole is about 4/5 of the bottom depth, the cone angle of the inverted cone is roughly 96°, and the tolerance of 0° ⁇ -2° is specially designed.
  • the best choice for the material of the conformal sample stage is pure copper.
  • Moissanite can be pressed into the inverted conical hole of the conformal sample stage by applying a pressure of 50Kgf ⁇ 250Kgf, forcing it to form surface contact with the inverted conical hole of the copper sample stage.
  • step 4 the Moissanite jewelry is placed together with the conformal sample stage in the diamond film deposition furnace for plasma treatment .
  • diamond film deposition methods such as DC Arc Plasma Jet (DC Arc Plasma Jet) CVD, microwave plasma CVD (MWCVD), and hot wire CVD (HFCVD) can be used for diamond film coating of Moissanite.
  • DC Arc Plasma Jet DC Arc Plasma Jet
  • MWCVD microwave plasma CVD
  • HFCVD hot wire CVD
  • plasma treatment employs DC arc plasma jet or microwave plasma.
  • the temperature of the plasma treatment is 700°C ⁇ 1000°C, and the time of the plasma treatment is 5 minutes ⁇ 30 minutes.
  • step 5 methane is introduced, and then the in-situ diamond film deposition is carried out.
  • the in-situ deposition of the diamond film described in step 5 includes the following two stages: nucleation and growth of the diamond film.
  • the concentration of methane in the nucleation stage is 3% ⁇ 10%, and the time is 5 ⁇ 20 minutes; the concentration of methane in the growth stage is 0.5% ⁇ 2%, and the time is 10 minutes ⁇ 120 minutes.
  • the pressure of the deposition furnace is set to 3kPa ⁇ 20kPa.
  • Example 1 Batch deposition of diamond film-coated Moissanite jewelry by DC arc plasma jet CVD system
  • Moissanite samples were first ultrasonically milled in a 30 nm diamond powder suspension for 2 h.
  • the Moissanite sample into a DC arc plasma CVD diamond film deposition furnace, and treat it in argon/hydrogen plasma for 5 minutes (Ar: 3slm; H2: 8slm; chamber pressure: 3 ⁇ 20kPa; plasma torch current: 90 ⁇ 120A; voltage: 97 ⁇ 110V; nozzle distance: 25mm).
  • the concentration of methane in the nucleation stage is 3% ⁇ 10%, and the time is 5 ⁇ 20 minutes; the concentration of methane in the growth stage is 0.5% ⁇ 2%, and the time is 10 minutes ⁇ 120 minutes.
  • the sample surface temperature is 700 ⁇ 1000°C.
  • the current is cut off to terminate the deposition of the diamond film, and the coated Moissanite sample can be taken out after cooling for 10 minutes.
  • the Moissanite sample of this diamond film coating has no difference in its degree of transparency and brilliance (fire color) and uncoated Moissanite (rough stone) under the naked eye or the low-magnification optical microscope photograph of illustration.
  • left side Adopt 5 micron and 1 micron mixed diamond powder ultrasonic grinding 2 hours pretreatment nucleation method and two-stage method (nucleation and growth) to prepare the surface morphology of diamond film coating Moissanite. Discrete large-sized grains appear, and the fire color of the coated Moissanite becomes poor;
  • the Vickers hardness calculated according to the indentation measurement data shown in the figure is as high as 117GPa, the average hardness calculated according to 10 test points is 84 ⁇ 7GPa, and the diamond hardness is 80-110GPa.
  • the diamond film-coated moissanite prepared by the technology of the invention has reached the hardness of diamond.
  • the scratch resistance ability of diamond film coating moissanite The scratch tester is used for testing, single crystal diamond stylus, the maximum scribing pressure is 20N, the scribing distance is 2mm, and the acoustic emission signal is recorded while scratching.
  • the optical microscope image shows that the scribe needle has been carved into the moissanite, forming obvious grooves, showing many discontinuous lateral cracks on both sides of the grooves, corresponding to a series of discontinuous acoustic emission peaks on the acoustic emission spectrum.
  • the thickness of the diamond film coating was measured under a field emission scanning electron microscope using a prefabricated fractured mosaic sample.
  • the diamond film coating thickness measured from the illustrated fracture images is 0.2–0.3 ⁇ m.
  • Example 2 Preparation of diamond film-coated Moissanite by microwave plasma CVD diamond film deposition equipment
  • the domestic 6KW grade stainless steel resonant cavity microwave plasma CVD diamond film deposition system is adopted.
  • the pretreatment process of Moissanite nuclei is exactly the same as that of DC arc plasma jet CVD.
  • hot-filament CVD can also be used to prepare diamond film-coated moissanite, due to the low temperature of the hot filament and insufficient gas activation, the concentration of atomic hydrogen is very low, which seriously affects the quality of the diamond film. Therefore, it is not recommended.

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Abstract

La présente divulgation concerne un ornement revêtu de film de diamant et un procédé de préparation d'un revêtement de film de diamant et appartient au domaine des revêtements chimiques. L'ornement revêtu de film de diamant, est caractérisé en ce qu'une surface d'un ornement de moissanite est plaquée d'un revêtement de film de diamant et le film de diamant a une taille moyenne de grain cristallin comprise entre 50 nm et 200 nm, une rugosité de surface inférieure à 10 nm et une épaisseur comprise entre 0,1 et 0,5 µm. Le procédé peut obtenir un revêtement de film de diamant uniforme et dense présentant de bonnes performances optiques sur la surface de l'ornement de moissanite. L'ornement de moissanite plaqué d'un film de diamant sur sa surface préparé selon le procédé peut présenter diverses propriétés physico-chimiques du diamant tout en maintenant les performances optiques (feu) de la moissanite et sa dureté de surface atteint la dureté du diamant, ce qui améliore considérablement la résistance aux rayures de la moissanite.
PCT/CN2021/118355 2021-09-13 2021-09-14 Ornement revêtu d'un film de diamant et procédé de préparation de revêtement de film de diamant WO2023035287A1 (fr)

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PCT/CN2021/135152 WO2023035429A1 (fr) 2021-09-13 2021-12-02 Procédé de dépôt d'un revêtement de film de diamant sur une surface de moissanite

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Citations (4)

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US20030224167A1 (en) * 2002-05-28 2003-12-04 Wright Less P. Hybrid gem System
US20060182883A1 (en) * 2005-02-17 2006-08-17 Suneeta Neogi Abrasion resistant coatings with color component for gemstones and such
WO2010009467A2 (fr) * 2008-07-18 2010-01-21 Serenity Technologies, Inc. Procédé pour former des revêtements de diamant nanocristallin sur des gemmes et d'autres substrats
CN108823550A (zh) * 2018-06-07 2018-11-16 深圳市金鑫丰利珠宝首饰有限公司 一种莫桑石饰品及在莫桑石饰品表面镀金刚石膜的方法

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US5882786A (en) * 1996-11-15 1999-03-16 C3, Inc. Gemstones formed of silicon carbide with diamond coating
JP2009100856A (ja) * 2007-10-22 2009-05-14 Nidec Sankyo Corp 装飾品
EP3479720B1 (fr) * 2017-11-07 2020-03-25 The Swatch Group Research and Development Ltd Procede de sertissage d'une pierre
CN110983298A (zh) * 2019-12-24 2020-04-10 中国科学院半导体研究所 一种用于微波等离子体化学气相沉积装置的样品台结构
CN111575795A (zh) * 2020-05-15 2020-08-25 南通大学 一种蓝色莫桑石的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030224167A1 (en) * 2002-05-28 2003-12-04 Wright Less P. Hybrid gem System
US20060182883A1 (en) * 2005-02-17 2006-08-17 Suneeta Neogi Abrasion resistant coatings with color component for gemstones and such
WO2010009467A2 (fr) * 2008-07-18 2010-01-21 Serenity Technologies, Inc. Procédé pour former des revêtements de diamant nanocristallin sur des gemmes et d'autres substrats
CN108823550A (zh) * 2018-06-07 2018-11-16 深圳市金鑫丰利珠宝首饰有限公司 一种莫桑石饰品及在莫桑石饰品表面镀金刚石膜的方法

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