CZ307885B6 - A method of producing a porous diamond layer and a thick porous diamond layer reinforced by nanofibres - Google Patents

A method of producing a porous diamond layer and a thick porous diamond layer reinforced by nanofibres Download PDF

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Publication number
CZ307885B6
CZ307885B6 CZ2017-500A CZ2017500A CZ307885B6 CZ 307885 B6 CZ307885 B6 CZ 307885B6 CZ 2017500 A CZ2017500 A CZ 2017500A CZ 307885 B6 CZ307885 B6 CZ 307885B6
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CZ
Czechia
Prior art keywords
diamond
nanofibres
porous
diamond layer
thick
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CZ2017-500A
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Czech (cs)
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CZ2017500A3 (en
Inventor
Vincent Mortet
Andrew Taylor
Ladislav Kavan
Otakar Frank
Zuzana Vlčková
Hana Krýsová
Václav Petrák
Original Assignee
Fyzikální Ústav Av Čr, V. V. I.
Ústav fyzikální chemie J. Heyrovského AV ČR, v. v. i.
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Application filed by Fyzikální Ústav Av Čr, V. V. I., Ústav fyzikální chemie J. Heyrovského AV ČR, v. v. i. filed Critical Fyzikální Ústav Av Čr, V. V. I.
Priority to CZ2017-500A priority Critical patent/CZ307885B6/en
Publication of CZ2017500A3 publication Critical patent/CZ2017500A3/en
Publication of CZ307885B6 publication Critical patent/CZ307885B6/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/26Deposition of carbon only
    • C23C16/27Diamond only
    • C23C16/272Diamond only using DC, AC or RF discharges
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/26Deposition of carbon only
    • C23C16/27Diamond only

Abstract

The present invention describes a method for producing a porous diamond layer (1, 6) and a porous diamond body (7) reinforced with nanofibers. The method comprises the step of inoculating diamond nanoparticles into nanofibers of any material capable of withstanding plasma-assisted deposition conditions. The inoculated nanofibers are then mixed into the sacrificial material. This mixture is then applied to the substrate (2) and dried to form a solid nanofiber / sacrificial composite film. The resulting composite film is then subjected to plasma assisted chemical deposition of diamond from the vapor phase under conditions where the sacrificial material is decomposed. These steps can be repeated to create a nanofiber reinforced porous diamond layer (6) of the desired thickness. Diamond can be doped with boron. Such conductive porous boron-doped diamond layers (1,6) serve for microelectronic (MEMS) applications where chemical stability is desired. Diamond doped porous diamond layers can be used as sensors, supercapacitors and / or filters for separating organic electrochemical materials.

Description

Technical field

The present invention relates to a method for producing a porous diamond layer by means of a plasma-enhanced chemical vapor deposition (PECVD), along with the decomposition of the sacrificial material. The invention also relates to a thick porous diamond layer reinforced with nanofibers, which can be obtained by the inventive method.

BACKGROUND OF THE INVENTION

Diamond is a material that has excellent electrochemical properties. Several methods have been developed for the production of porous (ie having a high surface to volume ratio) diamond electrodes, using either the top-down (etching) or bottom-up (growth on 3D substrates) principles.

Etching methods are limited by the diamond etching depth. The etching depth is limited by the isotropic effect of the oxygen plasma etching effect, which also etches the etching mask. the thickness of the porous material produced ends when the mask is completely consumed during the etching process. Metals (Al, Ni, and others) are generally used as the diamond etch mask. To increase the surface to volume ratio using the etching method, it is necessary to achieve a high density of diamond nanotubes or small diameter nanocolumns (several tens of nanometers), which requires the formation of an appropriate etching mask. Such metal masks can be produced by electron beam lithography, by self-emerging metal islands derived from annealed, several nanometer-thick layers of metal (e.g., Ni, Co, Au) [W. Smimov et al., Diam Relat Mater 19 (2010), 186], or a monolayer of metal nanoparticles. Diamond nanoparticles can also be used as an etching mask [N. Yang et al., Nano Lett 2008 (2008), 3572], The resulting porous materials further suffer from high electrical resistance of diamond rods or columns and limited conductivity of a boron-doped diamond [C. Hebert et al., Carbon 90 (2015), 102]

Methods of depositing a diamond thin film on 3D substrates with a high height to width ratio are limited by the quality and homogeneity of diamond inoculation as well as the unsatisfactory efficiency of CVD diamond deposition techniques. Of course, the top layers of 3D support structures (e.g., fiberglass filters) act as a mask for storing the diamond within the volume of the porous support structure (typically several micrometers deep). If the 3D support structure is not re-arranged after diamond deposition (see, e.g., F. Gao, W. Wolfer, C.E. Nebel, Carbon 80 (2014), 833), the increase in surface to volume ratio of the porous material produced is limited.

US 2013156974 discloses a method of making a thick porous diamond layer by plasma-assisted chemical deposition of diamond from the vapor phase of the sacrificial material and decomposing the sacrificial material. The method comprises arranging a layer formed of sacrificial material having a porous three-dimensional structure capable of progressive decomposition in contact with plasma and forming a diamond layer by plasma-assisted chemical deposition from the vapor phase.

- 1 GB 307885 B6

SUMMARY OF THE INVENTION

A novel method has been found combining diamond growth on substrates using a support structure on the one hand with decomposition of the sacrificial material on the other.

The method is characterized in that nanofibres of any material capable of withstanding plasma-assisted deposition conditions are inoculated with diamond nanoparticles, the inoculated nanofibers are then mixed into the sacrificial material, the resulting blend of sacrificial material with the inoculated nanofibres is then deposited on a substrate and dried for forming a solid composite film of inoculated fibers and sacrificial material. The resulting composite film is then subjected to plasma-assisted chemical deposition of diamond from the vapor phase under conditions where the sacrificial material is decomposed.

The sacrificial material is a material that is degraded in the plasma containing H and O, more particularly, that is degraded in the H-rich plasma used for diamond deposition by the PECVD method, preferably an organic polymer.

Nanofibres can be made of any material that is able to withstand PECVD deposition conditions (eg metal, carbon, silicon, S1O2, T1O2, AI2O3) and in any shape (eg whiskers, nanotubes, nanocolumns, nanotubes, straight or twisted nanofibers) ).

Nanofibers are inoculated with diamond and then dried. There are several methods for inoculating substrates with diamond to grow a thin diamond film, here inoculation using diamond nanoparticles [O.A. Williams, Chem. Phys. Lett. 445 (2007) 255]

The dry grafted nanofibers are then mixed into a sacrificial material, preferably an organic polymer, e.g. a viscous polymer solution or a precursor thereof.

The resulting mixture of seeded nanofibres in the polymer is then deposited in the form of a thin film on the substrate and solidified, e.g., dried, to form a solid composite film consisting of a polymer matrix filled with nanofibres. The thickness of the solid composite film depends on the coating method used, normally being several µm, generally between 1 and 100 µm. The substrate may be a metal, glass, ceramic or other material capable of withstanding PECVD deposition conditions.

This composite film is then subjected to plasma assisted chemical vapor deposition under diamond deposition conditions and simultaneous polymer decomposition. As a sacrificial material, the polymer, in contact with said plasma, is progressively decomposed with simultaneous diamond growth. The inoculated nanofibers withstand the deposition conditions and form a reinforcing skeleton.

The diamond can be intentionally doped with additives to obtain conductivity, if desired. Boron is known as a good alloying material. The resistivity can be reduced to several tens of mOhm.cm in the case of S1O2 nanofibres. By replacing S1O2 nanofibres with carbon nanofibres or metal whiskers, porous conductive diamond layers with more than 10 times (for multilayer carbon nanotubes) up to 1000 times (for metal whiskers with good conductivity) of higher conductivity can be obtained.

After carrying out the steps of the inventive method (ie coating the substrate with a polymer / nanofiber mixture, drying it, and PECVD diamond deposition) as described above, one or more layers of porous diamond may be formed in each case on the preceding layer. To this end, the steps of forming a film of a solid nanofiber / sacrificial composite material and subjecting it to plasma-assisted chemical deposition of a diamond from the vapor phase can be repeated to produce nanofiber-reinforced porous diamond layers or bodies of desired thickness, which may range from several µm to several mm. generally from 4 µm to 10 mm. Steps

Advantageously, the coating of the solid nanofiber / sacrificial composite coating and subjecting it to plasma-assisted chemical deposition of the diamond from the vapor phase is preferably repeated at least once, more preferably at least five times (to obtain a thickness of about 40 µm). To obtain very thick layers, said steps are repeated at least 12 times (thickness around 100 µm) or even more times.

The term layer as used herein is more general than the term thick layer and also includes the term film. The term body as used herein means a thick self-supporting layer.

The result of the invented process is a three-dimensional porous structure of nanofibres homogeneously coated and interconnected by diamond.

The thick porous diamond layer reinforced with nanofibres according to the invention consists of two or more layers of randomly deposited chopped nanofibres completely coated with diamond. The term randomly deposited means that the orientation of the fibers is the result of the step of applying a mixture of sacrificial material with inoculated nanofibers to the substrate. Accordingly, the length of the nanofibers in each layer may be greater than the thickness of the respective layer.

The individual nanofibres are connected at the points of mutual crossing and at the points of contact inside each layer by a diamond deposited on the respective fibers. There is no clear interface between two adjacent layers, more precisely, the fibers belonging to one layer are diamond bonded at the points of intersection and at the points of contact with the fibers belonging to the adjacent layer.

The thick porous diamond layer of the invention has a uniform porosity throughout the thickness. The porosity, expressed as a surface to volume ratio, is at least 6,000 cm, preferably at least 16,000 cm.

The thickness of the thick porous diamond layer of the invention is at least 4 µm. However, the advantages of the inventive method for producing a thick porous diamond layer are best utilized for producing thicker layers or bodies, e.g., 50 µm to 10 mm thick.

For some applications, freestanding thick porous diamond layers, i.e. self-supporting porous diamond bodies, are required. For this purpose, the thick diamond layers are separated from the substrate by dissolving or etching the substrate. The invention provides self-supporting, mechanically stable, nanofiber-reinforced porous diamond bodies several hundred micrometers thick, for example plates up to several mm thick.

The three-dimensional, nanofiber-reinforced porous structure according to the invention has controllable mechanical and electrical properties.

Clarification of drawings

In the attached drawings represents

Giant. 1 a porous diamond layer deposited on a diamond coated substrate,

Giant. 2 single nanofibers coated with diamond,

Giant. 3 is a thick porous diamond layer having a thickness several times greater than the porous diamond layer shown in FIG. 1; and

Giant. 4 self-supporting diamond body.

-3 CZ 307885 B6

DETAILED DESCRIPTION OF THE INVENTION

After carrying out the process of plasma-assisted chemical deposition of diamond from the vapor phase simultaneously with the decomposition of the sacrificial material in the method of the invention, a porous diamond layer 1 is obtained on the substrate 2. FIG. 1 illustrates a particular embodiment wherein the method of the invention comprises pretreating the substrate 2 with a diamond coating. As a result of this step, the substrate 2 is provided with a diamond film 5. The porous diamond layer 1 is arranged on this film 5 and consists of randomly oriented nanofibres 3 completely covered with diamond 4.

In the illustrated embodiment, the nanofibres 3 are nanotubes distributed with a random slope crosswise across the surface of the substrate. The nanofibres 3 form a three-dimensional support structure homogeneously coated and interconnected by diamond (shown only schematically, the diamond is not shown in Figs. 1, 3 and 4). It should be noted that the images are not to scale. Mutual proportions of fibers and layers resp. The layers are shown in the following detailed description.

Fig. 2 shows schematically a magnified individual nanofiber 3, as found in the porous diamond layer 1 according to the invention. The nanofibres 3 are completely covered by the diamond 4 deposited according to the invention by means of plasma-assisted chemical deposition of the diamond from the vapor phase together with the decomposition of the sacrificial material.

Fig. 3 shows schematically a thick porous diamond layer 6 reinforced with nanofibres produced by the method according to the invention. In this embodiment, the steps of forming the coating of the solid nanofiber / sacrificial material composite and subjecting it to plasma-assisted chemical deposition of the diamond from the vapor phase were performed 6 times (the first porous diamond layer 1 lies on the thin diamond film 5, and the 2nd to 6th layers 1). is always deposited on the preceding layer 1) to form a thick porous diamond layer reinforced by nanofibres 6 having a thickness approximately 6 times greater than the porous diamond layer 1 shown in Fig. 1.

For particular applications, the thick porous diamond layer 1 may subsequently be coated with a diamond thin film 5. FIG. 3 illustrates this embodiment with a diamond thin film 5 on both sides of a thick porous diamond layer 1.

In the embodiment shown in FIG. 4, no diamond thin film is present and the substrate is separated from the thick diamond layer. A self-supporting mechanically stable porous diamond body 7 is then obtained.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

S1O2 nanofibers from Elmarco sro, CZ are processed by ultrasound in D1 water at 400 W, with a utilization factor of 50%, for 10 minutes, using ultrasonic device UP400S with titanium sonotrode H22 from Hielscher-Ultrasound Technology, for separation and dispersion nanofibers (diameter 50 to 500 nm and length 5 to 20 micrometers). The suspension of dispersed chopped nanofibers is dried in air at high temperature (> 100 ° C) to evaporate water. The resulting powder is mixed with an aqueous colloid of diamond nanoparticles (0.2 g / L), sonicated, and dried to obtain diamond-coated nanofibers (same conditions as in the previous treatment). The dried grafted SiO2 nanofibres are then mixed with a polymer solution of ma-P 1210 (a solution of a positive tinting photoresist based on polymethyl methacrylate from Micro resist Technology GmbH, DE) at a concentration of about 80 mg fibers per milliliter to form a stable nanofiber suspension in the polymer solution. The suspension is centrifugally coated on a glass or silicon substrate 2, first coated with a thin diamond film 5, at 3000 rpm for 30 s. The samples coated with the nanofiber suspension in the polymer solution are then annealed on a hot plate at 110 ° C for 90 s for

Forming a homogeneous thin film of the polymer / nanofiber composite (about 4 microns thick). The sample is placed in a plasma assisted chemical vapor deposition (ASTeX 5010 from Seki Technotron, JP) diamond deposition system. The diamond coating is deposited under the following conditions: pressure: 50 mbar, microwave generator power: 1150 W, gas composition: 99.3% H2, 0.5% CH4 and 0.2% trimethyl borate (B / CtEE) with a total flow of 500 normal cm 3 per minute and a storage temperature of about 700 ° C. Coating with the nanofiber / polymer composite and diamond deposition is repeated repeatedly until the desired diamond layer thickness is achieved. In the 6-fold process of this coating process, a thick, nanofiber-reinforced, porous and conductive boron-doped diamond layer 1 is formed having a thickness of about 25 microns, a resistivity of about 60 mQcm (milliohm centimeter) and a surface to volume ratio of 16,000 cm.

Example 2

By reproducing the process described in Example 1, but with an increased number of steps, it is possible to obtain several hundred micrometers of thick, nanofiber-reinforced, self-supporting, mechanically stable porous diamond bodies 7, removing substrate 2 by wet chemical etching (e.g. using HF to etch glass substrate). or using HF + HNO3 to etch the silicon substrate).

Example 3

By reproducing the process described in Example 1, but by replacing S1O2 nanofibres with multilayer carbon nanofibres, it is possible to obtain porous conductive diamond layers 1, 6 with a resistivity of about 2 ηιΩ.αη. By replacing S1O2 nanofibres with metal whiskers, it is possible to obtain resistivity up to only 0.02 ηιΩχιιι.

Example 4

By reproducing the process described in Example 1, but depositing on the diamond coated substrate 2, a fully corrosion protected material with improved surface area is obtained, which is ideal for long-term operation as an electrochemical electrode (when the fiber material 1 and / or substrate 2 is electrically conductive).

Example 5

By reproducing the process described in Example 1, when depositing on the diamond coated substrate 2 and extending the deposition time in the last step, a closed surface and a porous diamond layer 6 interposed between two diamond closed and straight diamond thin films 5 are obtained. This material with controllable mechanical properties can be used for microelectronic (MEMS) applications (eg sensors).

Industrial applicability

The layers 1, 6 and / or the bodies 7 produced according to the present invention can be used, due to their controllable mechanical properties, as chemically inert electrodes for demanding electronic sensing and processing devices. The film comprising at least one layer may serve for microelectronic (MEMS) applications for which chemical stability is desired. In particular, the porous conductive boron-doped diamond foils can be used for applications in supercapacitors.

The porous diamond layers can also serve as filters for separating organic electrochemical substances from water.

-5 CZ 307885 B6

The present invention is not limited to the specific applications described herein, but may serve various purposes.

The process according to the present invention represents a cheap and efficient solution for the production of the novel porous diamond layers 1, 6 or bodies 7 described above.

PATENT CLAIMS

Claims (19)

  1. A method for producing a porous diamond layer by plasma assisted chemical deposition of diamond from a vapor phase simultaneously with decomposition of sacrificial material, characterized in that nanofibers of a material capable of withstanding plasma assisted deposition conditions are inoculated with diamond nanoparticles wherein the nano fibers are carbon or metal whiskers, inoculated nanofibres are then mixed into the sacrificial material, the resulting mixture of sacrifice material with inoculated nanofibres is then applied to a substrate and dried to form a solid composite film of inoculated nanofibers and sacrificial material, and the resulting solid composite film is then subjected to a plasma-supported chemical deposition of diamond from the vapor phase under conditions where the sacrificial material is decomposed.
  2. Method according to claim 1, wherein the application of the mixture of sacrificial material with nanofibres is carried out by centrifugal coating or dip coating or spray coating, preferably by centrifugal coating.
  3. The method according to claim 1 or 2, wherein said steps of forming a solid composite film of inoculated nanofibers and sacrificial material and subjecting it to plasma-assisted chemical deposition of diamond from the vapor phase are repeated at least once more to form a nanofiber reinforced porous diamond layer of desired thickness.
  4. Method according to any one of the preceding claims, wherein the sacrificial material is an organic polymer that is decomposed in a hydrogen rich plasma.
  5. Method according to any one of the preceding claims, wherein the diamond is doped with an admixture, preferably boron.
  6. Method according to any one of the preceding claims, wherein all the nanofibres are carbon nanofibres or metal whiskers.
  7. The method of any preceding claim, wherein the method comprises the step of pretreating the substrate with a diamond coating.
  8. The method of any preceding claim, wherein the method comprises the subsequent step of coating the porous diamond layer with diamond.
  9. The method of any preceding claim, wherein the method comprises the step of separating the diamond layer from the substrate by dissolving or decomposing the substrate.
  10. Thick porous diamond layer reinforced by nanofibres, characterized in that it consists of at least two layers (1) of randomly deposited nanofibres (3) completely coated with diamond (4), wherein the nanofibres are carbon or metal whiskers, the average length of nanofibres in each layer (1) is greater than the thickness of the layer (1), wherein the individual nanofibres (3) are joined by diamond (4) at the points of intersection and at the points of contact inside said layers (1) as well as between said layers (1); wherein the thickness of the thick porous diamond layer (6) is at least 4 µm and the surface to volume ratio of the thick porous diamond layer (6) is at least 6000 cm
    -6GB 307885 B6
  11. The thick nanofiber reinforced porous diamond layer according to claim 10, wherein its thickness is at least 16 µm and its surface to volume ratio is at least 1200 cm
  12. Thick porous nanofiber reinforced diamond layer according to claim 10, which consists of at least ten layers (1) of randomly deposited nanofibres (3) completely coated with diamond (4), the thickness of which is at least 50 µm.
  13. Thick porous nanofiber reinforced diamond layer according to claim 10 or 11, wherein the diamond (4) is doped with an admixture, preferably boron.
  14. A thick porous diamond layer reinforced by nanofibres according to claim 13, having a resistivity lower than 40 m.q.cm, wherein all nanofibres (3) are carbon nanofibres.
  15. The thick nanofiber-reinforced porous diamond layer according to claim 13, having a resistivity of less than 0.4 m.cm, wherein the nanofibres (3) are metal whiskers.
  16. A thick nanofiber-reinforced porous diamond layer according to any one of claims 10 to 15, which is supported on a substrate (2).
  17. The thick nanofiber reinforced porous diamond layer according to claim 16, wherein the substrate (2) and / or the surface of the thick porous diamond layer is coated with a thin diamond film (5).
  18. The thick nanofiber-reinforced porous diamond layer according to any one of claims 10 to 15, which forms a self-supporting body (7).
  19. The thick nanofiber reinforced porous diamond layer according to claim 18, wherein at least one of its surfaces is coated with a thin diamond film (5).
CZ2017-500A 2017-08-29 2017-08-29 A method of producing a porous diamond layer and a thick porous diamond layer reinforced by nanofibres CZ307885B6 (en)

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CZ2017-500A CZ307885B6 (en) 2017-08-29 2017-08-29 A method of producing a porous diamond layer and a thick porous diamond layer reinforced by nanofibres

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CZ2017-500A CZ307885B6 (en) 2017-08-29 2017-08-29 A method of producing a porous diamond layer and a thick porous diamond layer reinforced by nanofibres
PCT/CZ2017/050053 WO2019042484A1 (en) 2017-08-29 2017-11-01 Method of manufacturing a porous diamond layer and a nanofiber supported thick porous diamond layer

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CN110230044A (en) * 2019-07-12 2019-09-13 中国工程物理研究院激光聚变研究中心 It is the method that counterfeit template prepares porous boron-doped diamond electrode with nano-diamond powder

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US20160230310A1 (en) * 2015-02-09 2016-08-11 Saeed Alhassan Alkhazraji Process of manufacturing pure porous diamond

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Title
Kondo, T.: et al: Diamond & Related Materials 72 (2017) 13 – 19, zveřejněný on-line 11. 12. 2016 *
Petrák, V., et al: Carbon 114 (2017) 457 – 464, dostupný online od 8. 12. 2016) ISSN: 0008-6223 *
Zanin, H., et al: Applied Materials & Interfaces (2016), 6, 990 – 995 *

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