• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a vapor phase diamond deposition equipment comprising: - a vacuum reactor (3) comprising a reaction chamber connected to a vacuum source, - a substrate holder (5) disposed in the reactor, which can move along three axes and turn on itself. According to the invention, the equipment comprises a plasma source which has an active source located in the reaction chamber. This source can move along three axes or be attached to an articulated arm, in order to make diamond deposits on the inner side of hollow parts.
    公开号:CH710472A1
    申请号:CH01942/14
    申请日:2014-12-15
    公开日:2016-06-15
    发明作者:Provent Christophe；Rats David
    申请人:Neocoat Sa；
    IPC主号:
    专利说明:

    Technical area
    The present invention relates to the field of diamond deposition on the inner surface of a substrate, particularly to polycrystalline diamond deposition in the vapor phase. The thickness of the diamond layer deposited in the present invention will generally be less than 2000 nm and the deposition is carried out at a temperature below 500 ° C, preferably between 200 and 450 ° C.
    State of the art
    Diamond is a material with exceptional properties such as its high hardness, its high Young's modulus or its high thermal conductivity. It can be synthesized in a thin layer using the chemical vapor deposition (CVD) method by thermally or plasma activating a gaseous mixture containing at least one precursor of carbon and hydrogen. The activation of the gas phase makes it possible to create radical species such as atomic hydrogen or the methyl radical with a concentration sufficient to ensure the rapid growth of a diamond layer of high crystalline quality.
    [0003] Various applications of the diamond layers require the coating of the interior of tubular or hollow-shaped substrates with a diamond layer, which can not, or very difficultly, be achieved with the techniques generally used.
    The substrates of tubular or hollow shapes to be coated may consist of a material which is altered in structure or shape by the temperatures used by the techniques generally used for the synthesis of diamond.
    This is for example the case with a thermal activation of the reaction gas mixture by hot filament (HFCVD for Hot Filament Chemical Vapor Deposition). This technique allows deposits over large areas (> 0.5m2) but the deposition temperature is much higher than 400 ° C, usually above 750 ° C. Therefore, when the substrate cools after deposition, it undergoes thermal deformations at a different coefficient of the diamond. Differential deformation frequently causes stresses or defects in the diamond layer or the interface with the diamond layer.
    Another solution is to deposit a layer of polycrystalline diamond by conventional microwave plasma technology, which allows to deposit polycrystalline diamond of good quality, but only on small surfaces (<0.05 m <2>), not the interior of a tube-type hollow substrate and at temperatures above 400 ° C (usually> 600 ° C), resulting in thermal stresses similar to those mentioned above.
    The two aforementioned techniques use working pressures greater than 10 mbar generating convection phenomena unfavorable to the diffusion of radical species in spaces such as the interior of a hollow substrate or generating a low uniformity in thickness of the deposit on large substrates.
    In addition, to have a uniform deposition, it is important that the radical species can be uniformly generated directly at or near the hollow substrate, in the immediate vicinity of the surface to be coated, including in relatively small spaces.
    Finally, to be able to deposit a layer of polycrystalline diamond without altering the intrinsic properties of the material to be coated or its geometric tolerances, it is important to deposit it at low temperature to minimize the thermal deformations and stresses resulting from thermal behavior. different between the diamond and the substrate.
    The use of a plasma technology with a coupling of microwave energy through surface waves, which reduces the deposition temperature to a value close to 100 ° C., is known. The use of a plasma technology using a matrix of coaxial plasma applicators is also known, which also makes it possible to reduce the deposition temperature to a value close to 100 ° C. Such a technology is described in the patent WO 2014 154 424. However, the known devices use a two-dimensional plasma sheet, and therefore do not allow to apply a regular layer of diamond on the inner surface of a hollow substrate such as for example a tube, a sheath, a duct or a hollow piece, tube type, closed at one of its ends.
    It is known to generate a plasma inside a tube for depositing diamond inside thereof. However, the substrate material must be transparent to microwaves, which limits its use to materials such as silica or alumina.
    The present invention aims to solve these problems.
    Disclosure of the invention
    More specifically, the invention relates to an equipment and a deposit method implementing this equipment, as mentioned in the claims.
    Brief description of the drawings
    Other details of the invention will appear more clearly on reading the description which follows, made with reference to the accompanying drawing in which:<tb> fig. 1 <SEP> is a view representing a diamond deposition equipment according to the invention,<tb> figs. 2, 3 and 5 <SEP> provide illustrations of the different possible configurations of the deposition equipment in order to obtain uniform diamond deposits regardless of the geometry and shape of the internal surface of the substrate, and<tb> fig. 4 <SEP> gives illustrations of examples of substrates that can be advantageously covered with diamond by a process according to the invention
    Embodiment of the invention
    As mentioned above, it is possible to produce polycrystalline diamond deposits at low temperature by advantageously implementing the microwave plasma vapor phase chemical deposition technology using microwave waves. surface, on various substrates, which will be defined below. However, the equipment of the state of the art does not make it possible to make deposits inside a substrate.
    According to the invention, deposits are made on this kind of substrate by implementing the microwave plasma deposition technology using a point source plasma (EPS) source with equipment as proposed in FIG. 1.
    This deposition system 1 comprises a vacuum reactor 2, a substrate holder 3 and an elementary plasma source, here a coaxial applicator 4, housed in the wall of the vacuum reactor 2 or at the end of a maintaining arm, and the substrate 5 placed on the substrate holder 3. Preferably, the coaxial applicator has, at its end located in the reaction chamber, a quartz or alumina window, defining an active zone located in the the reaction chamber. This type of applicator is commercially available and does not need to be described in detail.
    With the use of an elementary plasma source (EPS), it is possible to lower the working pressure to a value less than 1 mbar, preferably between 0.1 and 1 mbar. Such a pressure makes it possible to promote the phenomena of diffusion of the chemical species and thus to have very homogeneous deposits on the circumference of the internal surface of the substrate in which the elementary source is placed.
    It can also work with a temperature between 100 ° C and 500 ° C, which limits the thermal deformation of the substrate, particularly with a metal substrate. Thus, during the cooling of the coated substrate, the deformation differential between the substrate and the diamond layer is reduced, thereby limiting the mechanical stresses at the interface of the materials, without having to resort to intermediate layers.
    In order to obtain an even layer along the substrate, the substrate holder can move along the axis of the substrate defined by z as shown in FIG. 2 or it is the plasma source which can also be moved as shown in FIG. 3.
    In order to obtain a uniform layer on the circumference of the substrate, the substrate holder or the plasma source can move along the axes perpendicular to the axis of the substrate defined by x and y, but also have a rotational movement. on himself.
    In order to obtain a uniform layer on a complex surface defined by several changes of slope as shown in FIG. 4, the plasma source can be placed on an articulated arm so that its active area remains equidistant from the surface to be coated regardless of the shape of the inner surface of the workpiece. Fig. 5 shows the configuration of the deposition reactor with an articulated arm 6.
    By implementing this installation, it can thus perform a polycrystalline diamond deposit on a hollow part as proposed in FIG. 5, This hollow part is defined by its internal dimension, d, the substrate to be coated whose size is between 30mm and 400mm, and its length, D, whose dimension between 10 and 2000mm. The inner surface may be flat (Figure 4.1), convex (Figure 4.2), concave (Figure 4.3), complex (Figure 4.4), smooth, structured or microstructured.
    Such a part can be made of a material chosen from the following materials: refractory metals and derivatives, transition metals and derivatives, stainless steels, titanium-based alloys, superalloys, cemented carbides, silicon-based alloys, glasses oxides (fused silica, alumina), organic polymers, semiconductors III-V or III-VI, other materials coated with a thin layer of the above-mentioned materials.
    According to a particular example, 1, the substrate is stainless steel 316L grade, tubular as described in FIG. 4.1 (d = 80 mm and D = 500 mm), only inoculated by a method of the state of the art and without any additional pretreatment or prior deposition of an intermediate layer, such as a diffusion barrier.
    The substrate is placed on a substrate holder rotating on itself at a speed of 20 rpm and moving along the z axis at a linear speed of 1mm / s. The deposition reactor is described in FIG. 2.
    A 200 nm layer of polycrystalline diamond is deposited using the chemical vapor deposition method assisted with an elementary plasma source (EPS) by means of an installation as described above with the following deposition conditions. :Filing time = 20 hoursSubstrate temperature = 300 ° C,Working pressure = 0.5 mbar.
    A control of the thickness of the deposited layer (measurement on metallographic sections) and the quality of the deposit (measurement by Raman spectrometry) shows that the variation of uniformity (calculated by the formula = (min-max) / average) is less than 10% over the entire area deposited.
    According to a particular example, 2, the substrate is fused silica, of concave shape as described in FIG. 4.2 (d = 60 mm and D = 300 mm), only inoculated by a method of the state of the art and without it being necessary to apply additional pretreatment or prior deposition of an intermediate layer.
    The substrate is placed on a substrate holder rotating on itself at a speed of 20 rpm and moving along the z axis at a linear speed of 1 mm / s, and the x and y axes at a linear speed. of 1mm / s, to maintain a distance of 30 mm between the center of the plasma and the surface to be coated.
    A layer of 500 nm of polycrystalline diamond was deposited using the chemical vapor deposition method assisted with an elementary plasma source (EPS) by means of an installation as described above with the conditions of deposition. following:Filing time = 22 hoursSubstrate temperature = 400 ° C,Working pressure = 0.25 mbar.
    A control of the thickness of the deposited layer (measurement on metallographic sections) and the quality of the deposit (measurement by Raman spectrometry) shows that the variation of uniformity (calculated by the formula = (min-max) / average) is less than 10% over the entire area deposited.
    In a particular example, 3, the substrate is a titanium base alloy (Ti-4AI-6V) of convex shape as described in FIG. 4.3 (d = 75 mm and D = 250 mm), only inoculated by a method of the state of the art and without any additional pretreatment or prior deposition of an intermediate layer, such as a diffusion barrier.
    The substrate is placed on a substrate holder rotating on itself at a speed of 20 rpm and moving along the z axis at a linear speed of 1 mm / s, and the x and y axes at a linear speed. of 1 mm / s to maintain a distance of 37.5 mm between the center of the plasma and the surface to be coated.
    A layer of 300 nm of polycrystalline diamond was deposited using the method of chemical vapor deposition assisted with an elementary plasma source (EPS) by means of an installation as described above with the conditions of deposition. following:Filing time = 15 hoursSubstrate temperature = 400 ° C,Working pressure = 0.20 mbar.
    A control of the thickness of the deposited layer (measurement on metallographic sections) and the quality of the deposit (measurement by Raman spectrometry) shows that the variation of uniformity (calculated by the formula = (min-max) / average) is less than 10% over the entire area deposited.
    According to a particular example, 4, the substrate is in inconel 625, of complex shape as described in FIG. 4.4 (d = 90 mm and D = 1500 mm), only inoculated by a method of the state of the art and without any additional pretreatment or prior deposition of an intermediate layer, such as a diffusion barrier.
    The substrate is placed on a substrate holder rotating on itself at a speed of 20 rpm. The plasma source, here a coaxial applicator, is mounted on an articulated arm, in order to maintain a distance of 30 mm between the center of the plasma and the surface to be coated. The deposition reactor is described in FIG. 5.
    A layer of 300 nm of polycrystalline diamond was deposited using the chemical vapor deposition method assisted with an elementary plasma source (EPS) by means of an installation as described above with the conditions of deposition. following:Filing time = 40 hoursSubstrate temperature = 400 ° C,Working pressure = 0.20 mbar.
    A control of the thickness of the layer deposited (measurement on metallographic sections) and the quality of the deposit (measurement by Raman spectrometry) shows that the variation of uniformity (calculated by the formula = (min-max) / average) is less than 10% over the entire area deposited.
    According to a particular example, 5, an engine cylinder (d = 81 mm and D = 165 mm) in high speed steel (type H56-5-2C), inoculated by a method of the state of the art. The substrate is placed on a fixed substrate holder and the plasma source is rotated on itself at a speed of 20 rpm and moves along the z axis at a linear speed of 1 mm / s. The deposition reactor is described in FIG. 3.
    A 200 nm layer of nanocrystalline diamond is deposited using the chemical vapor deposition method assisted with an elementary plasma source (EPS) by means of an installation as described above with the following deposition conditions. :Filing time = 8 hoursSubstrate temperature = 300 ° C,Working pressure = 0.5 mbar.
    By nanocrystalline diamond is meant polycrystalline diamond, having a grain size of between 1 and 100 nm, typically around 20 nm, to obtain an average roughness of less than 200 nm, preferably less than 50 nm.
    A control of the thickness of the layer deposited (measurement on metallographic sections) and the quality of the deposit (measurement by Raman spectrometry) shows that the variation of uniformity (calculated by the formula = (min-max) / average) is less than 10% over the entire area deposited.
    Thus, by implementing the chemical vapor deposition technology using an elementary plasma source (EPS) by means of an installation as proposed above, it is possible to produce a layer of polycrystalline diamond whose thickness is between 50 nm and several μm and whose uniformity variation (calculated by the formula = (min-max) / average) is less than 10% over the entire deposited surface. It is possible to produce on the internal surfaces of parts, at low pressure and at low temperature, deposits whose grain size between 1 and 50 nm, typically around 10 nm, making it possible to obtain an average roughness of less than 100 nm, preferably less than 20 nm.
    权利要求:
    Claims (14)
    [1]
    A vapor phase diamond deposition apparatus using at least one cold plasma source comprising:A vacuum reactor (3) comprising a reaction chamber connected to a vacuum source,A substrate holder (5) arranged in the reactor,characterized in that it comprises one or devices (s) allowing the end of the cold plasma source to be positioned inside hollow parts.
    [2]
    2. Equipment according to claim 1, which comprises a plasma applicator which has an active source located in the reaction chamber and characterized in that the point source of plasma is a coaxial applicator.
    [3]
    3. Equipment according to claim 2, wherein the coaxial plasma applicator is fixed on a device as mentioned in claim 1 and can be stationary, move in one, two or three axes, or be attached to the end of an articulated arm, but always positioned in such a way that the active end and the plasma which is derived from it can be located inside hollow parts.
    [4]
    4. Equipment according to claim 1, wherein the substrate holder can move in one, two or three axes and turn on itself,
    [5]
    5. Equipment according to claim 2, characterized in that the coaxial applicator has, at its end located in the reaction chamber, a quartz or alumina window, defining the active zone.
    [6]
    6. Polycrystalline diamond deposition process implementing equipment according to one of claims 1 to 5, characterized in that it is carried out at a temperature between 100 and 500 ° C.
    [7]
    7. polycrystalline diamond deposition process according to claim 6, characterized in that it is carried out at a pressure between 0.1 and 1mbar.
    [8]
    8. deposition process according to one of claims 6 and 7, characterized in that it is formed on the inner surface of hollow parts of the tube type, cylinder, box, or any other free form part having an inner portion of hollow.
    [9]
    9. deposition process according to claim 8, characterized in that the inner walls of the substrate may be concave, convex, smooth, macrostructured, microstructured.
    [10]
    10. Method according to claim 9, characterized in that the substrate is selected from the following materials: silicon and silicon-based compounds, diamond, refractory metals and derivatives, transition metals and derivatives, stainless steels, titanium-based alloys , superalloys, cemented carbides, polymers, ceramics, glasses, oxides (fused silica, alumina), semiconductors III-V or II-VI.
    [11]
    11. The method of claim 9, characterized in that the substrate may be made of any material coated with a thin layer of materials cited in claim 10.
    [12]
    12. Part obtained by a method according to one of claims 6 to 11, characterized in that it comprises a polycrystalline diamond deposition having a thickness whose value is between 50 and 2000 nm and whose variation in uniformity ( calculated by the formula = (min-max) / average) is less than 20% over the entire area deposited.
    [13]
    13. Part according to claim 12, characterized in that the diamond deposition is nanocrystalline diamond type having a grain size of between 1 and 100 nm, typically around 20 nm, to obtain an average roughness of less than 200 nm. preferably less than 50 nm.
    [14]
    14. Part according to claim 12, characterized in that the diamond deposition is of the microcrystalline diamond type having a grain size of between 10 and 1500 nm, typically around 100 nm.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP2714961A1|2014-04-09|Method for depositing layers on a glass substrate by means of low-pressure pecvd
    FR2928939A1|2009-09-25|METHOD FOR PRODUCING NANOSTRUCTURES ON A METAL OXIDE SUBSTRATE, METHOD FOR DEPOSITING THIN LAYERS ON SUCH A SUBSTRATE, AND DISPOSITION OF THIN LAYERS
    EP1636399A1|2006-03-22|Coating for a mechanical part, comprising at least one hydrogenated amorphous carbon, and method of depositing one such coating
    JP2002265296A|2002-09-18|Diamond thin film and manufacturing method therefor
    FR2803603A1|2001-07-13|DIAMOND COATING IN THE FORM OF THIN OR THIN FILM RESISTANT TO EROSION AND CORROSION, AND APPLICATIONS THEREOF
    CH710472A1|2016-06-15|vapor phase diamond deposition equipment assisted by plasma for coating the inner surface of hollow parts.
    Yang et al.2021|Research on the fabrication and anti-reflection performance of diamond-like carbon films
    EP2832899A1|2015-02-04|Diamond coating and method for depositing such a coating
    EP2675936B1|2014-10-29|Device for synthesising a nanostructured composite material, and associated method
    EP2695967A1|2014-02-12|Process to synthetize a nanostructured composite material and associated dispositive.
    FR2896807A1|2007-08-03|THIN MULTILAYER STRUCTURE, PIECE COMPRISING SAME AND ITS DEPOSITION METHOD
    EP2978871B1|2017-04-05|Method for a diamond vapor deposition
    Hao et al.2006|Nano-crystalline diamond films synthesized at low temperature and low pressure by hot filament chemical vapor deposition
    FR2678956A1|1993-01-15|DEVICE AND METHOD FOR DEPOSITING DIAMOND BY DCPV ASSISTED BY MICROWAVE PLASMA.
    EP2376671A1|2011-10-19|Method for making diamond composite materials
    Mallik et al.2009|High vacuum tribology of polycrystalline diamond coatings
    EP0653394A1|1995-05-17|Surface treatment of carbon material to ensure the adhesion of a diamond coating and diamond coated articles prepared therefrom
    CH710471A1|2016-06-15|Equipment diamond vapor deposition by hot filament for coating the inner surface of hollow parts.
    Abadi et al.2019|Studying the effects of plasma produced species on the optical characteristics and bonding structure of diamond-like carbon films deposited by direct current unbalanced magnetron sputtering
    Boughaba et al.1999|Characterization of tantalum oxide films grown by pulsed laser deposition
    JP2008056955A|2008-03-13|Carbon film deposition method
    Sousani et al.2018|Thermal stability of germanium-carbon coatings prepared by a RF plasma enhanced chemical vapor deposition method
    EP3283292B1|2019-05-08|Method for preparing a metallic part in such a way as to improve the measurement of the temperature of same by optical pyrometry during pressurisation of same under uniaxial deformation conditions
    Spiesser et al.2007|Surface free energy of cubic boron nitride films deposited on nanodiamond
    CH707800A2|2014-09-30|A method of vapor deposition of diamond and equipment for performing this method.
    同族专利:
    公开号 | 公开日
    CH710472B1|2019-02-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE10060886A1|1999-12-10|2001-07-05|Saint Gobain Ceramics|Device and method for coating non-flat surfaces of objects with a diamond film|
    US20020170495A1|2001-05-17|2002-11-21|Ngk Insulators, Ltd.|Method for fabricating a thin film and apparatus for fabricating a thin film|
    FR2847911A1|2002-12-02|2004-06-04|Lorraine Inst Nat Polytech|Reinforcement of the inner wall of a hole emerging from a hollow body by chemical vapor phase deposition of diamond, notably for reinforcing wire drawing dies|
    EP1447459A2|2003-02-17|2004-08-18|Ngk Insulators, Ltd.|A method and system for producing thin films|
    US20070218660A1|2006-03-14|2007-09-20|Hiroaki Yoshida|Diamond film formation method and film formation jig thereof|
    DE102010000940A1|2010-01-15|2011-07-21|Krones Ag, 93073|Device for plasma-treating a container for inner coating of the container, comprises an evacuatable treatment chamber, an electrode to generate plasma in the container, and a transport unit to move the container into the treatment chamber|
    US20120231177A1|2011-03-11|2012-09-13|Southwest Research Institute|Depositing Coatings In Long Hollow Substrates Using A Heated Center Electrode|WO2021069620A1|2019-10-11|2021-04-15|Neocoat Sa|Cvd reactor for manufacturing synthetic films and methods of fabrication|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH01942/14A|CH710472B1|2014-12-15|2014-12-15|Plasma assisted vapor phase diamond deposition equipment for coating the inner surface of hollow parts.|CH01942/14A| CH710472B1|2014-12-15|2014-12-15|Plasma assisted vapor phase diamond deposition equipment for coating the inner surface of hollow parts.|
    [返回顶部]