EP2984202A1 - Procédé et dispositif de formation d'une structure sur un substrat - Google Patents

Procédé et dispositif de formation d'une structure sur un substrat

Info

Publication number
EP2984202A1
EP2984202A1 EP14724502.1A EP14724502A EP2984202A1 EP 2984202 A1 EP2984202 A1 EP 2984202A1 EP 14724502 A EP14724502 A EP 14724502A EP 2984202 A1 EP2984202 A1 EP 2984202A1
Authority
EP
European Patent Office
Prior art keywords
substrate
laser
plasma
powder
laser beam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14724502.1A
Other languages
German (de)
English (en)
Inventor
Stefan Nettesheim
Dariusz Korzec
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Maschinenfabrik Reinhausen GmbH
Scheubeck GmbH and Co
Original Assignee
Maschinenfabrik Reinhausen GmbH
Maschinenfabrik Reinhausen Gebrueder Scheubeck GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Maschinenfabrik Reinhausen GmbH, Maschinenfabrik Reinhausen Gebrueder Scheubeck GmbH and Co KG filed Critical Maschinenfabrik Reinhausen GmbH
Publication of EP2984202A1 publication Critical patent/EP2984202A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K31/00Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by any single one of main groups B23K1/00 - B23K28/00
    • B23K31/02Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by any single one of main groups B23K1/00 - B23K28/00 relating to soldering or welding
    • 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K10/00Welding or cutting by means of a plasma
    • B23K10/02Plasma welding
    • B23K10/027Welding for purposes other than joining, e.g. build-up welding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
    • B23K26/14Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
    • B23K26/144Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor the fluid stream containing particles, e.g. powder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
    • B23K26/34Laser welding for purposes other than joining
    • B23K26/342Build-up welding
    • 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134Plasma spraying

Definitions

  • the invention relates to a method for constructing at least one structure on a surface of a substrate.
  • the structure is made up of a powder as a layer.
  • the invention relates to a device for constructing at least one structure on a surface of a substrate.
  • a machining head with a nozzle is provided, which serves to form a low-temperature plasma jet.
  • a powder feed serves to supply a powder into the low temperature plasma jet or into the plasma to form the low temperature plasma jet.
  • Plasmajet applied to a surface of a substrate to be coated.
  • this technique can only achieve line widths not less than about 1 millimeter for the applied layer.
  • the edges of the lines are not particularly sharp, which is due to the inhomogeneous, one
  • masks must be provided for each desired shape of the layer, even if the number of substrates to be coated is small. It is known from DE 10 2008 001 580 A1 to apply the material for a layer as a dispersion of nanoparticles to a surface of a substrate.
  • the nanoparticles thus applied are thermally post-treated by means of a CO 2 laser in order to obtain a desired electrical conductivity and transparency of the layer.
  • Non-thermally treated areas of the layer are easily removed from the surface of the substrate while the thermal treated areas of the layer adhere well, cf. Zieris R et al., 2003, Characterization of coatings deposited by laser-assisted atmospheric plasma, Materials Park, Ohio: ASM International, pp. 567-572, ISBN: 0-87170-785-3.
  • the laser irradiation does not contribute to the formation of finer structures here.
  • EP 0 903 423 A2 and similar to DE 197 40 205 B4, describe a method for applying a layer by means of plasma spraying. In this case, at least one continuous laser beam through the spray jet with predetermined
  • the process is generally a high temperature process using a plasma torch that is based on the processing of materials
  • Plasma coating process using a plasma torch together with a laser.
  • a laser beam By a laser beam, the surface to be coated is locally melted, a plasma jet rushes to the laser beam and carries the in
  • Plasma contained coating material in the melt Plasma contained coating material in the melt.
  • Plasma spraying is found in S.E. Nielsen, "Laser fusing - combining laser and plasma spraying techniques for surface improvements”.
  • the powder particles are present in a molten or molten state, in the latter case as droplets.
  • material of the powder particle In order for sufficient adhesion between such a powder particle and a surface of the substrate to be formed, it is necessary for material of the powder particle to be distributed on the surface; namely, an increase in the contact area between the material of the powder particle and the surface of the substrate improves the adhesion of the powder particle to the substrate.
  • the surface of the substrate is too cold, at least thermal conductivities of the substrate and the molten powder material, a temperature difference between the powder particle and the substrate, the heat transfer between the substrate and the molten powder material, the melting temperature of the powder and a play Heat capacity of the powder particles roll, so the molten solidifies
  • the basic idea of the invention consists in at least one
  • Targeted heat input here means that only one, possibly spatially narrow, defined area of the surface of the substrate to be coated to build the structure, the laser beam is exposed, and that the laser irradiation also takes place temporally immediately in the environment of the coating, so that Damage to the substrate is avoided by an unnecessarily prolonged action of the laser on a location of the substrate as well as a large outflow of the amount of heat introduced from the defined area before the coating that the heat input can not show the desired effect.
  • the application of the material for the structure to the surface of the substrate on which the structure is to be built up by coating the surface is carried out by a Plasmajet to which the material is added as a powder.
  • This plasma jet is a low-temperature plasma jet.
  • the delivery of the powder to the plasma of the plasma jet can be carried out by any person skilled in the art
  • the powder may also be supplied to the plasma before the plasma jet is formed; Also, a supply of the powder to the gas from which the plasma is generated, is conceivable
  • Low-temperature Plasmajet and moves the substrate relative to each other, so that at least the defined area of the surface of the substrate in which the structure is to be built, is applied to the powder.
  • At least one laser beam which is directed onto the substrate is used, as already stated. This results in a Laser incidence region of the at least one laser beam on the substrate;
  • the substrate may also already be charged with powder, wherein the laser beam then primarily meets the powder located on the substrate.
  • the low-temperature plasma jet strikes the substrate in a plasma impact area.
  • the at least one laser beam is directed onto the substrate in such a way that a defined relative position is given between the laser impact area and the plasma impact area.
  • Laser impact area is always within the defined, to be coated area and is moved over this area. The extent of heat input within the
  • Laser impact area can be influenced, for example, by the power of the laser beam and the speed with which the laser is guided over the substrate surface.
  • the defined relative position between the laser impact area and the plasma impact area is such that the Laser impact area is outside the plasma impact area and is not yet loaded with powder.
  • the powder particles meet in the molten or molten state on the surface of the
  • Temperature difference between the powder particles and the substrate is reduced within the defined range. As a result, the heat flow from the powder particles to the substrate is reduced, and the solidification of molten material of the powder particles is delayed against powder particles applied outside the defined range.
  • the prerequisite for the method in this embodiment is that the substrate absorbs the laser light to an extent sufficient to achieve the required heat input into the substrate.
  • the at least one laser beam is guided so that it does not traverse the low-temperature plasma jet.
  • the at least one laser beam is guided so that it passes through the low-temperature Plasmajet. Therefore, in this embodiment of the method, an additional heat input into the laser beam in the plasma jet can be made through powder particles, provided that these powder particles are able to absorb the laser light. The additional heat input into the powder particles contributes to a delay in the solidification of the molten material of these powder particles after they hit the defined area of the surface of the substrate.
  • the laser incident region overlaps the plasma impact region.
  • the laser impact area is located wholly or partially within the plasma impact area. Therefore, in this embodiment, at least part of the laser radiation is incident within the
  • a prerequisite is that the powder particles the Laser light absorb, and the method can be applied even if the substrate is so largely transparent even for the laser light used that a sufficient heat input into a defined region of the surface of the substrate by direct absorption of laser light through the substrate is not possible.
  • the powder within the laser impact area absorbs the
  • Delayed powder particles against a powder applied outside the defined range of powder particles Delayed powder particles against a powder applied outside the defined range of powder particles.
  • Plasma impact area is also located, which also outside the
  • Plasma impact area is located. In this case the laser incidence area is not coherent.
  • Laser impact area smaller than a diameter of the plasma impact area. Since laser beams can be focused on smaller diameter areas than is possible with plasma jets, it is possible with this embodiment of the method to clearly show structures with typical size scales, eg lines with a width below the size scales or widths that can be generated with a plasma jet without a mask. With this embodiment of the method, it is quite possible to produce line widths down to 50 micrometers, while with the plasma jet alone, without masks, hardly any line widths below 1 millimeter are possible.
  • a laser beam can be reduced to a smaller area
  • Diameter focus as a plasma jet when constructing structures of correspondingly small dimensions, for example of lines having a width smaller than the diameter of the plasma impact area, the plasma jet initially also applies powder to areas of the substrate which lie outside the defined area to be coated and thus outside of the area the interaction of laser beam and plasma jet built-up on the substrate structure.
  • the particles deposited outside the structure at best are weakly attached to the substrate. Such particles can be easily removed from the surface of the substrate, e.g. blown off so that only the structure built up on the substrate remains.
  • the particles which have been applied outside the defined area to be coated and which rapidly solidify are also already swept away by the gas flow of the plasma jet itself.
  • the method is not limited to planar substrates, but can be applied to arbitrarily designed substrates.
  • the device according to the invention for constructing at least one structure on a surface of a substrate has a machining head which has a nozzle for forming a low-temperature plasma jet.
  • Low-temperature plasma may serve as a known plasma generator.
  • the device according to the invention further comprises a powder feed, with which the powder from which the structure is to be constructed, the plasma jet itself or the plasma from which the Plasmajet is to be formed first, or the gas from which the plasma is to be generated fed is.
  • the processing head according to the invention at least one laser emitter assigned. The assignment is such that a laser beam from the laser emitter can be directed onto the substrate such that a defined relative position between a laser incidence region of the laser beam on the substrate and a plasma impingement region of the low-temperature plasma jet on the substrate is achievable. For example, the laser emitter so on
  • the laser beam is emitted at a defined angle to the central axis of the Plasmajets, resulting in a defined relative position between the laser incident and the plasma impact area.
  • the laser emitter is on the processing head
  • the laser may be, for example, a semiconductor laser.
  • the laser light can be guided for at least one laser beam through at least one light guide to the processing head and be coupled there out of the at least one light guide.
  • the laser emitter is on
  • Processing head supported end of the light guide in addition to a coupling-out optics, to extract the laser light from the light guide.
  • the laser emitter may also be adjustably mounted on the machining head. The adjustment can be made manually by an operator, or via actuators as a result of control signals issued by a user of the
  • At least one movable reflector is provided to guide the laser beam across the substrate.
  • the at least one movable reflector can be controlled such that the laser impact area describes the desired path on the substrate, within the defined area to be coated. In such an embodiment is a fixed
  • Laser beam and the Plasmajet are understood, more generally the relative course of the Plasmajets and the at least one laser beam, from which also the relative position between the plasma impact area on the surface of the
  • Substrate and the laser impact area on the surface of the substrate determined.
  • this relative position can be adapted.
  • the device may further comprise a device with which a
  • a robot arm may be provided to move the machining head relative to the substrate, alternatively, for example, a gantry robot may be used. It is also possible to place the substrate on a movable table or to have it moved by a robot relative to the plasma jet.
  • the device according to the invention is suitable for this purpose
  • FIG. 1 shows a first embodiment of the method in which the laser beam is guided in front of the plasma jet.
  • Figure 2 shows a plan view of a surface of a substrate
  • FIG. 3 shows a second embodiment of the method in which the laser beam passes through the plasma jet.
  • Figure 4 shows a third embodiment of the method in which the laser beam is directed into the plasma jet.
  • FIG. 5 shows a plan view similar to FIG. 2, but for the embodiment of FIG. 4.
  • FIG. 6 shows an embodiment of the device according to the invention.
  • FIG. 7 shows a further embodiment of the device according to the invention.
  • FIG. 1 shows a first embodiment of the method according to the invention for constructing a structure 2 on a substrate 100.
  • a powder 20 is added to a low-temperature plasma jet 10, which powder is conveyed through the plasma jet 10 on a substrate
  • the powder 20 is here supplied to the plasma jet 10 by a powder feed 21 shown only schematically.
  • the plasma jet 10 emanates from a processing head 1 1, which is in communication with a plasma generator, not shown here.
  • a laser beam 30, generated here by a laser 31 is directed onto the surface 1 of the substrate, where it defines a laser incidence region 35 (see FIG. 2) in a region which has not yet been exposed to powder 20 by the plasma jet 10.
  • Processing head 1 1, laser 31, and powder feed 21 is guided in the direction of the arrow 50 relative to the surface 1 of the substrate 100.
  • the powder 20 is supplied to the plasma jet 10 outside the processing head 11. However, this does not matter
  • the powder 20 may be supplied to the plasma ultimately forming the plasma jet 10 in any manner known to those skilled in the art of low temperature plasma spraying.
  • the laser beam 30 is directed directly to the substrate 100 through the laser 31 and the laser 31 is moved relative to the surface 1.
  • the impact of the laser beam 30 on the substrate 100 and the movement of the laser beam 30 relative to the surface 1 is relevant, regardless of where the laser beam 30 is generated and how it is ultimately directed to the substrate 100.
  • Figure 2 shows a plan view of a surface 1 of a substrate 100; the
  • Top view corresponds to an embodiment of the method as shown in FIG. Shown is the laser impingement region 35, ie the region in which the laser beam 30 (see FIG. 1) strikes the substrate 100;
  • the illustrated circular shape of the laser impingement region 35 is not a limitation of the invention.
  • a portion of a defined region 37 to be coated is also shown.
  • the laser impingement region 35 is directed in the direction of the arrow 50 over the defined region 37 causing heat input into the substrate 100.
  • the laser impingement region 35 leaves on movement in the direction of the arrow 50 a preheated region 36 on the surface 1 of the substrate 100, which is not yet charged with powder 20 (see FIG. 1).
  • Laser incidence region 35 and plasma incidence region 15 have a defined relative position R to one another. Between the plasma impact area 15 and the laser impact area 35 is the preheated, not yet acted upon with powder 20, area 36.
  • Plasma impingement 15, in the direction of arrow 50 moves over the surface 1, so 20 powder 20 is deposited along a track S of the plasma impingement region 15 on the surface 1; During this movement, the plasma impact area 15 also passes over the respective preheated area 36, since the plasma jet 10 tracks the laser beam 30, which causes the plasma impact area 15 to follow the laser impact area 35.
  • good adhesion can form between the powder 20 deposited in the preheated region 36 and the surface 1 of the substrate 100, as, inter alia, a temperature difference between the powder particles in the plasma jet 10 and the preheated region due to the preheating of the region 36 36 is reduced.
  • the structure 2 here in the form of a line with a width 3, constructed.
  • areas 16 outside the preheated area 36 is one
  • Line widths 3 are possible, which are significantly smaller than those achievable with a low-temperature plasma jet alone, ie without the use of a laser beam
  • FIG. 3 largely corresponds to FIG. 1. In the one shown in FIG. 1,
  • the laser beam 30 is directed through the Plasmajet 10 on the surface 1 of the substrate 100.
  • the laser beam 30 strikes outside of the plasma jet 10 on the surface 1 of the substrate 100.
  • a laser incidence region 35 defined by the laser beam 30 on the substrate 100 lies in front of the plasma incidence region 15 in the direction of movement 50, so that the plasma jet is also in this form 10 the laser incident region 35 is tracked.
  • the laser beam 30 here can also heat powder particles which pass through the laser beam 30 within the plasma jet 10. This additional heating of the powder particles leads to a delay of the solidification of the powder particles after their impact on the substrate 100, as already explained above.
  • FIG. 4 shows a further embodiment of the method which is similar to that shown in FIG. The vast majority of the illustrated elements have already been discussed in connection with FIG. Plasmajet 10 and laser beam 30 have been shown larger than Figure 1, for reasons of clarity.
  • FIG. 4 also shows a density profile 22 of the powder 20 in the plasma jet 10 and the plasma impingement area 15 determined by the density profile 22
  • Laser beam 30 is applied to a portion of the surface 1 in this embodiment of the substrate 100, which is already charged with powder 20. More specifically, the laser beam 30 is directed into the plasma jet 10 so as to meet a front edge 22F of the density profile 22, as seen in the direction 50 of a relative movement of the plasma jet 10 to the surface 1. As a result, a thin powder layer 2d which has already been deposited on the substrate 100 in this front flank 22F is included
  • FIG. 5 shows a plan view of the surface 1 of the substrate 100, as corresponds to an embodiment of the method shown in FIG. All shown
  • FIG. 2 is a corresponding illustration for an embodiment of the method shown in FIG.
  • the laser incidence region 35 lies within the
  • Plasma incidence area 15 A preheated area 36 as in FIG. 2 is not present here, since the heat input in the laser incidence area 35 takes place in powder already deposited on the surface 1, as shown in FIG.
  • the prerequisite for the embodiment illustrated in FIGS. 4 and 5 is that the powder 20 is able to absorb the laser light sufficiently.
  • the substrate 100 may be transparent to the laser light.
  • FIG. 6 shows an embodiment of the device 300 according to the invention.
  • a machining head 1 1 has a nozzle 12 for forming a plasma jet from a plasma.
  • a plasma generator known to the person skilled in the art can be used.
  • a laser 31 is mounted at the processing head 1 1.
  • the laser 31 is adjustable, so that in particular the above-discussed relative position R between the plasma incidence region 15 and 35 Laseraufmachining Suite can be adjusted.
  • the laser may be a semiconductor laser.
  • FIG. 7 shows a further embodiment of the device 300 according to the invention. Some of the elements shown have already been described in connection with FIG. 6 discussed.
  • One end 33e of a light guide 33 is in a holder 33h on
  • a coupling-out optical system 34 for decoupling laser light from the light guide 33 is further provided.
  • the coupling-out optical system 34 is supported on the machining head 11 in this embodiment.
  • the laser light is fed into the light guide 33 by a laser 31 in a manner known to those skilled in the art.
  • the laser may be a semiconductor laser.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Coating Apparatus (AREA)
  • Nozzles (AREA)

Abstract

L'invention concerne un procédé de formation d'au moins une structure (2) sur un substrat (100). Une poudre (20), dont doit être constituée la structure (2), est appliquée sur la surface (1) du substrat (100) par un jet de plasma à basse température (10). Au moins un faisceau laser (30) provoque un apport de chaleur dans le substrat (100) et/ou dans la poudre (20), à l'intérieur d'une zone d'incidence (35) du laser sur le substrat (100). L'apport de chaleur retarde la solidification des particules de poudre partiellement ou complètement fondues dans le jet de plasma (10) sur le substrat (100), et rend ainsi possible la formation d'une bonne adhérence entre la poudre appliquée (20), et par conséquent la structure (2) qui en résulte, et le substrat (100). L'invention concerne en outre un dispositif (300) pour la mise en oeuvre dudit procédé.
EP14724502.1A 2013-04-12 2014-04-04 Procédé et dispositif de formation d'une structure sur un substrat Withdrawn EP2984202A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013103693.7A DE102013103693A1 (de) 2013-04-12 2013-04-12 Verfahren und Vorrichtung zum Aufbau einer Struktur auf einem Substrat
PCT/IB2014/060422 WO2014167468A1 (fr) 2013-04-12 2014-04-04 Procédé et dispositif de formation d'une structure sur un substrat

Publications (1)

Publication Number Publication Date
EP2984202A1 true EP2984202A1 (fr) 2016-02-17

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Country Status (5)

Country Link
US (1) US9649729B2 (fr)
EP (1) EP2984202A1 (fr)
JP (1) JP2016518523A (fr)
DE (1) DE102013103693A1 (fr)
WO (1) WO2014167468A1 (fr)

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DE102013103693A1 (de) 2014-10-16
WO2014167468A1 (fr) 2014-10-16
US9649729B2 (en) 2017-05-16
JP2016518523A (ja) 2016-06-23

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