EP1866462A2 - Electrode de traitement de surface - Google Patents
Electrode de traitement de surfaceInfo
- Publication number
- EP1866462A2 EP1866462A2 EP06726175A EP06726175A EP1866462A2 EP 1866462 A2 EP1866462 A2 EP 1866462A2 EP 06726175 A EP06726175 A EP 06726175A EP 06726175 A EP06726175 A EP 06726175A EP 1866462 A2 EP1866462 A2 EP 1866462A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- deposition
- solution
- reduction
- cavity
- 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- Withdrawn
Links
Classifications
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
Definitions
- the present invention relates to an object surface treatment electrode.
- This electrode is particularly suitable for the implementation of a process for depositing metal by oxidation-reduction on objects, producing, for example, a deposit of gold on solid or hollow microspheres, respectively called microbeads and microballoons, made of polymer or glass. , used especially in the context of physics studies on power lasers. It can also be used to metallize metal balls or not, used in various fields such as the manufacture of thermal or pressure sensors, biomedical dielectric sensors or optical sensors.
- the electrode can also be used for performing electrochemical polishing, chemical, or other surface treatments such as degreasing, anodizing, phosphating or nitriding.
- microballoons or microbeads used as targets.
- These microballoons made for example based on polymer or glass, are spheres or quasi-spheres each having a central cavity limited by a wall, while the microspheres are solid spheres or quasi-spheres.
- these microballoons or microbeads have a diameter of about 100 microns and the wall of each microballoon is about a few micrometers.
- the microballoons must be covered with a metal layer, such as for example gold, of about 10 microns thick.
- the deposition of metal on the microballoon must have a thickness as homogeneous as possible, have a density as close as possible to the theoretical density of the deposited metal, have no defect of health matter and have a surface roughness not exceeding one hundred nanometers. These parameters are difficult to control because they can vary from one microballoon to another.
- each of the microballoons individually so as to be able to characterize with as much precision as possible the deposit obtained on the microballoons. It is the same for microbeads. Different deposition techniques exist and can be used for the metallization of an object.
- PVD Physical Vapor Deposition
- Oxidation-reduction deposition techniques are broken down into two different categories:
- the chemical deposit by immersion which is to provide the electrons necessary for the reduction of the metal to be deposited by an exchange between two pairs of redox.
- the reducer that oxidizes to generate the electrons may be either the metal to be coated, it is called in this case chemical deposition by displacement, or a reduced ionic form soluble to oxidize, it is called chemical deposition by reduction.
- These electrons can also be provided by electrical contact between the object to be metallized and another less noble metal having a stronger propensity to oxidize, the object and the other metal being immersed in the same metal solution to be deposited: it is called chemical deposition by contact or battery effect.
- the deposit begins as soon as the pieces are immersed in the deposition solution, the oxidation-reduction reaction then taking place naturally, without external supply of current;
- electrolytic deposition which consists in supplying the electrons necessary for the reduction of the metal to be deposited by performing an electrochemical reaction between an electrode and the metal to be deposited contained in the deposition solution.
- the object to be metallized is negatively biased by connecting it to a negative pole of a current source.
- a positive pole of the current source is connected to an anode which is also immersed in the deposition solution which serves as an exchange site for the combined oxidation reaction.
- the current source can deliver DC current, but also alternating current: it is called pulsed current deposition. In this case, the shape of the electrical signal is imposed and controlled. Then, successively and according to the sign of the current, a reduction or oxidation reaction takes place on the surface of the object to be metallized, which can in certain cases improve the deposition.
- the chemical deposition processes by displacement or by reduction make it possible to obtain a deposition thickness having excellent homogeneity. But they do not allow, for some metals, especially for gold, to obtain deposit thicknesses greater than one micrometer.
- Electrolytic deposition processes make it possible to obtain deposits without limit of thickness. But, for the metallization of an object of very small size, and with the existing devices, it is difficult to reproducibly control the homogeneity of the thickness of the deposit because of the distribution of the current lines.
- Electrolytic deposition processes require the use of a current supply, allowing the object to be metallized to be crossed by the electrolysis current, or a holding support, fixed to the surface of the object to be metallized. This has the effect of creating a hole in the deposit thickness after the separation of the current and the object, which is not conceivable given the requirement of no health defect material on the surface of the deposit.
- Microballoons can thus remain stuck together and the deposit can be damaged by successive shocks.
- current density gradients remain unavoidable from one microballoon to another, thus making it difficult to control and reproduce the homogeneity of the thickness of the deposit and the roughness of the deposit.
- several microballoons are simultaneously present in the aqueous solution, it is impossible to follow them in a unitary manner and thus to be able to characterize the deposition precisely. The characterization of the deposit then depends essentially on the geometric disparity of the microballoons.
- the aim of the present invention is to propose an electrode for the implementation of, for example, a method of metal deposition by oxidation-reduction, making it possible to perform, depending on the metal to be deposited and the deposition technique used. , any thickness of deposit with, in terms of homogeneity, roughness, lack of health matter, approaching the theoretical density of the deposited metal, a quality superior to that obtained with the methods and devices of the prior art.
- the present invention also aims to provide an electrode for the implementation of various methods of treating surface objects, such as electrochemical or chemical polishing, for removing material from the object with, in terms of homogeneity, roughness, material health defect, a quality superior to that obtained with the methods and devices of the prior art.
- the present invention provides an electrode for surface treatment of at least one object, comprising at least one cavity enclosing the object to be treated during the treatment and having a geometry ensuring the object a free movement, this cavity being delimited by a wall having at least one opening communicating the interior of the cavity with a treatment solution in which the electrode is immersed during the surface treatment.
- Said cavity may be substantially cylindrical and have a diameter greater than about 50 to 100 micrometers with respect to a maximum dimension of the object.
- an electrode is used which, by ensuring a free movement to the object, avoids leaving a defect either in the metallization carried out, either in the material removed, due to the presence of the support for holding or supplying current during treatment.
- This electrode also makes it possible to avoid the problems encountered with the devices metallising several objects simultaneously, these problems being described above in the state of the prior art.
- this reduction electrode makes it possible to obtain any deposit thickness, unlike the existing devices implementing a method of chemical deposition by stack effect.
- the wall of the cavity is provided with an orifice for the introduction of the object, this orifice being intended to be closed by a plug.
- the opening of the wall of the cavity may have dimensions ensuring 'circulating the plating solution in the cavity while preventing the object out of the cavity.
- the aperture may be a slot having a width that is smaller than the radius of an object of spherical or quasi-spherical shape.
- the electrode may include a plurality of cavities so as to simultaneously accommodate a plurality of objects, the cavities being able to be substantially superposed relative to each other in columns or arranged substantially next to one another in a ring.
- the electrode may be formed of a body connected to a removable head which comprises the cavity, it It is then easy to change the head when the latter is, for example, covered with an excessive layer of the metal to be deposited.
- an insulating coating such as a dielectric sheath, for example to protect the metal that is deposited.
- the head may be formed of two parts joined to each other, a first part connected to the body forming a chamber provided with a gas supply port and a second part comprising the cavity, these two parts communicating with each other. one with the other.
- the electrode may be a reduction electrode for carrying out a process of metal deposition by oxidation-reduction on the metallized object at least at the surface, the treatment solution then being a deposition solution.
- the electrode may be made at least partly of brass if the metal to be deposited is gold.
- the electrode When the deposit is a chemical deposit by displacement or reduction, the electrode may be at least partly made of a non-metallic material such as polyvinyl chloride (PVC) or tetrafluoroethylene polymer to avoid any corrosion by local battery effect between the object to be metallized and the electrode.
- PVC polyvinyl chloride
- the cavity it is advantageous for the cavity to have a geometry that ensures the object electrical contact with the wall as frequently as possible during the free movement of the object in the cavity.
- the electrode may be an oxidation electrode for implementing a method of electrochemical polishing by oxidation-reduction of the metallized object at least at the surface, said electrode being able to be at least partly made of an electrically-based material. conductor and not interfering in the redox process involved, the cavity being able to have a geometry providing the object with electrical contact with the wall as frequent as possible during its free movement in the cavity.
- the electrode may be at least partly - made from a material inert to the treatment solution.
- the present invention also relates to a method of surface treatment of at least one object comprising the steps of:
- the surface treatment may be a metal deposition by oxidation-reduction reaction on the object at the less metallized surface
- the treatment solution may be a deposition solution containing ions of the metal to be deposited
- the surface treatment electrode may be a reduction electrode as described above.
- the reduction electrode may be at least partly made of a non-metallic material such as polyvinyl chloride or tetrafluoroethylene polymer to prevent corrosion by local battery effect between the object to be metallized and the electrode which would then cause a deterioration of the interior of the electrode and therefore a risk of deterioration of the object to be metallized.
- a non-metallic material such as polyvinyl chloride or tetrafluoroethylene polymer
- the method may further comprise a step of dipping into the deposition solution, in addition, at least one oxidation electrode made of a metal having a reducing power greater than that of the metal to be deposited, this oxidation electrode being electrically connected to the reduction electrode directly or via a coulometer.
- the method may further comprise a step of dipping into the deposition solution, in addition, at least one oxidation electrode made from a metal that does not pollute the deposition solution. during its oxidation, this oxidation electrode being electrically connected to the reduction electrode via a current source.
- the metal of the oxidation electrode can be immersed in a conductive solution placed in a closed container by at least one ionic junction allowing electrical contact between the conductive solution and the deposit solution without mixing them.
- the ionic junction may be a glass frit or a gelatinous ionic junction.
- the metal of the oxidation electrode may be aluminum.
- the surface metallization of the object is electronegativally and adhesively compatible to receive the metal in the deposition solution.
- the surface metallization of the object may be chosen from among gold, copper and nickel.
- the metal to be deposited may be chosen from gold, copper, nickel, or any other depositable metal in aqueous solution.
- the thickness of the deposit may be between about a few nanometers and a few tens of micrometers.
- the surface treatment may be a redox electrochemical polishing of the metallized object at least at the surface
- the surface treatment electrode may be an oxidation electrode for the implementation of a redox electrochemical polishing process, said which process may further comprise a step of dipping into the treatment solution, in addition, at least one metal reduction electrode, said reduction electrode being electrically connectable to the oxidation electrode via a source current.
- a gas may be injected into the cavity during deposition, causing the object to move into the cavity.
- the injection can be preferably intermittently.
- the gas may preferably be a neutral gas so as not to change the pH of the deposition solution. It is possible to heat the deposition solution during the deposition.
- the object to be metallized may be made of polymer, glass or any other solid material, for example ceramic or metal.
- the object to be metallized may be a microballoon or a microbead.
- the wall of the microballoon may have a thickness of a few micrometers.
- the diameter of the object can be between about 100 micrometers and 2 millimeters.
- the treatment solution may be an aqueous solution based on potassium aurocyanide.
- the present invention also relates to a device for implementing a method of surface treatment of an object, comprising: a container for containing a treatment solution;
- the treatment process may be a redox reaction metal deposition process
- the treatment solution may be a deposition solution
- the surface treatment electrode may be a reduction electrode for the implementation of a deposition method.
- oxidation-reduction metal deposition process The device may further comprise at least one oxidation electrode to be placed in the receptacle and to be electrically connected to the reduction electrode either directly or via a coulometer, when the process is a chemical deposition process. by stack effect.
- the device may further include at least one oxidation electrode to be placed in the vessel and electrically connect to the reduction electrode via a current source when the deposition process is an electroplating process.
- the device comprises means for heating the treatment solution. It is possible to provide means for controlling the temperature of the treatment solution, such as a electronic thermometer thermocouple to dive into the treatment solution.
- the device comprises gas injection means in the gas supply port of the treatment electrode.
- the gas injection means may for example be at least one capillary connecting the orifice to a peristaltic pump or to a gas circuit comprising a flow control valve. It can be envisaged that the stirring means are magnetic, with ultrasound or else a device coming to tap the treatment electrode.
- FIG. 1A is an example of an object to be metallized
- FIG. 1B is an example of an object, metallized on the surface, to be metallized
- FIG. 2 is an example of a surface metallization device
- FIG. 3A is a diagram of a treatment electrode, object of the present invention, according to a first embodiment
- FIG. 3B is a diagram of a treatment electrode, object of the present invention, according to a second embodiment
- FIG. 4 is a diagram of a treatment electrode head, object of the present invention, of which the two parts are assembled;
- FIG. 5 is a diagram of a treatment electrode head, object of the present invention, the two parts are not assembled;
- FIG. 6 is a diagram of the first part of a head of a treatment electrode, object of the present invention.
- FIG. 7 is a diagram of the second part of a head of a treatment electrode, object of the present invention.
- FIG. 8 is a front view of the second part of a head of a treatment electrode, object of the present invention.
- FIG. 9 is a diagram of a treatment electrode, object of the present invention, according to a third embodiment
- FIG. 10 is a diagram of a treatment electrode, object of the present invention, according to a fourth embodiment
- FIG. 11 is a diagram of a device, object of the present invention for the example implementation "of a chemical deposition method by displacement or by reduction, also object of the present invention;
- FIG. 12 is a diagram of a device, object of the present invention, for the implementation for example of a method of depositing electrolytic, also object of the present invention
- FIG. 13 is a diagram of a device, object of the present invention, for the implementation for example of a method of chemical deposition by stack effect, also object of the present invention;
- FIG. 14 is a diagram of an oxidation electrode used during a battery-effect chemical deposition method, object of the present invention.
- FIG. 15 is a graph showing the electrical intensity flowing in the oxidation electrode, with or without insulation of the metal of the electrode with the deposition solution, during chemical deposition by stack effect, according to a process object of the present invention
- FIG. 16 is a graph representing the deposition rate during chemical deposition by stack effect, according to a method that is the subject of the present invention, with and without a coulometer connecting the two electrodes;
- FIG. 17 is a graph showing the deposition rate of several chemical deposits by stack effect, according to a method that is the subject of the present invention.
- FIG. 18 is a graph showing several measurements of the deposition thickness produced by stack effect, according to a method of the present invention.
- Identical, similar or equivalent parts of the different figures described below bear the same numerical references so as to facilitate the passage from one figure to another.
- the different parts shown in the figures are not necessarily in a uniform scale, to make the figures more readable.
- the object 1 to be metallized is a microballoon 1.
- the microballoon 1 is a sphere or quasi-sphere having a central cavity 2 bounded by a wall 3. Its diameter is generally between about 100 micrometers and 2 millimeters. The thickness of the wall 3 of the microballoon 1 is generally a few micrometers.
- the object 1 to be metallized could also be a microbead, that is to say a sphere or quasi-solid sphere. But the object 1 to be metallized could be any piece, non-spherical, more complex geometry and a larger size.
- the microballoon 1 is made of glass or polymer, but it could be made of another material, for example a metal.
- This type of object 1 is extremely fragile and therefore requires a lot of care during handling thereof.
- the object 1 to be metallized is not metallic, before starting a process for depositing metal, object of the present invention, the object 1 must at least be metallized surface 4, as shown in FIG IB.
- the metal used for this surface metallization 4 is compatible from the point of view of the electronegativity and the adhesion to receive the deposition of the metal according to the deposition method, object of the present invention, described below.
- This surface metal 4 may for example be gold, copper or nickel.
- this surface metallization 4 is made by a surface metallization device 6, shown in FIG. 2.
- This device 6 comprises a cup 7.
- This cup 7 is intended to receive one or more objects 1 to surface metallize simultaneously. In this example, only the object 1 is metallized on the surface.
- the cup 7 is placed in a physical vapor deposition chamber 8 (known by the English name PVD for Physical Vapor Deposition).
- the device 6 comprises a piston 9 controlled by a signal generator 10 for vibrating the cup 7 during the surface metallization 4 of the object 1.
- the signal generator 10 sends control signals to the piston 9 which then gives The vibrations of the cup 7 then move the object 1 throughout the metallization.
- a very homogeneous metallization layer 4 is thus obtained over the entire surface of the object 1.
- the thickness of metal obtained is for example between about 50 nanometers and 100 nanometers. 50 nanometers is about the minimum thickness necessary to ensure sufficient adhesion of the metal layer to be deposited thereafter.
- an electrolytic deposition technique For these four techniques, the principle is to achieve between the metal in the deposition solution, for example gold, and a less noble metal having a reducing power greater than that of the metal to be deposited, for example of the aluminum, a galvanic couple.
- the less noble metal is immersed in the deposition solution containing ions of the metal to be deposited. Since aluminum has a reducing power greater than that of gold, aluminum will transform in ionic form in the deposition solution according to reaction (1):
- the gold deposit thus continues, as long as the two parts of the galvanic pair are physically and electrically bonded, that is to say as long as there is gold in the deposit solution and as long as the aluminum is transforms into ionic form.
- FIG. 3A An exemplary embodiment of this reduction electrode 11 is shown in FIG. 3A. It comprises at least one cavity 23, visible in FIG. 7. This cavity 23 is intended to enclose the object 1 during the deposition. It has a geometry ensuring the object 1 a free movement. This cavity 23 is delimited by a wall 24, visible in Figure 7 also.
- the cavity 23 has a geometry providing to the object 1 makes electrical contact with the wall 24 as frequently as possible during its free movement in the cavity 23.
- the cavity 23 is substantially cylindrical in shape, which is a shape adapted to contain a spherical or quasi-spherical object 1.
- the inner diameter of this cylinder about 50 microns to 100 micrometers larger than the maximum dimension of the object 1, for example between about 150 micrometers and 2.1 millimeters in the case of a microballoon 1, is important because if it is too small, object 1 remains stationary in the cavity 23 during deposition, and if it is too large, the contact with the wall 24 will be random, uncommon and the deposition rate uncontrollable during electroplating or battery effect.
- the reduction electrode 11 may take the form of at least one body 12 connected to a removable head 13.
- the body 12 is a metal rod of substantially cylindrical shape.
- the reduction electrode 11 is preferably made of a non-metallic material such as PVC (polyvinyl chloride) or tetrafluoroethylene polymer, in order to avoid corrosion of the electrode.
- PVC polyvinyl chloride
- tetrafluoroethylene polymer tetrafluoroethylene polymer
- the head 13 preferably consists of two parts 14, 15 joined together.
- FIG. 4 is a diagram of the head 13 of which the two parts 14,
- This assembly can for example be a screwing.
- FIG. 5 shows the head 13 with the two parts 14, 15 unassembled.
- the first part 14 is formed of a cylinder 16.
- This first part 14 forms a chamber 17, visible in FIG. 6.
- a first base 18 of this cylinder 16 is open and has a thread 19 extending partially inside. of the chamber 17.
- This chamber 17 has a port 20 which passes through a side wall of the cylinder 16.
- This aperture 20 serves as gas feed used during deposition. The role of this gas will be explained later in the description of the invention.
- a threaded cylindrical portion 22 is contiguous with a second base 21 of the cylinder 16, opposite to the first base 18. This threaded cylindrical portion 22 makes it possible to screw the first portion 14 to the body 12 of the reduction electrode 11.
- the second part 15 is shown in FIG. 7.
- the cavity 23 is in this second part 15.
- the cavity 23 communicates with the deposition solution via at least one opening 25.
- the head 13 has two openings 25, as shown in Figure 8 which is a front view of the second portion 15.
- Each opening 25 is a slot made on the entire length of the cavity 23.
- This opening 25 allows to widely communicate the deposition solution with the interior of the cavity 23 when the electrode 11 is immersed in the deposition solution.
- the dimensions of this opening 25 must guarantee the movement of the deposition solution in the cavity 23 while preventing the object 1 from leaving the cavity 23.
- the slots have a width less than the radius of the cavity.
- an opening 25 may be of substantially circular shape.
- Figure 3B shows a reduction electrode 11 according to an embodiment different from that shown in Figure 3A. In FIG. 3B, the reduction electrode 11 has several openings 25 distributed along the length of the cavity 23.
- the second portion 15 has, opposite the cavity 23, a threaded portion 26. This threaded portion 26 is screwed into the threaded portion 19 of the first portion 14.
- a seal 27 is inserted between these two parts 14 and 15 to seal the head 13.
- the removable head 13 can be easily changed when it is covered with a too thick layer of the metal to be deposited.
- the wall 24 of the cavity 23 is provided at one of its ends with an orifice 28 for the introduction of the object 1 into the cavity 23.
- This orifice 28 is intended to be closed by a plug 55 during the deposition, as illustrated in Figure 7, so that the object 1 does not not at the other end of the cavity 23, an opening 29 communicates the chamber 17 of the first part 14 with the interior of the cavity 23 when the two parts 14 and 15 of the head 13 are assembled together.
- This opening 29 is dimensioned so that the object 1 can not pass through.
- the length of the body 12 of the electrode 11 is adapted so that, during the deposition, the object 1 is completely immersed in the deposition solution.
- the reduction electrode 11 may comprise a plurality of cavities 23.
- Each of these cavities 23 may receive an object 1 to be metallized.
- These cavities 23 may for example be arranged substantially next to each other, thus forming a crown.
- FIG. 9 represents a reduction electrode 11 comprising a plurality of cavities 23 arranged substantially next to one another. It is also conceivable that these cavities 23 are superimposed on each other in columns.
- Figure 10 shows the second portion 15 of the head 13 having a plurality of cavities 23 superimposed relative to each other in column. Each cavity 23 is separated from its adjacent cavities 23 by a wall 56.
- the walls 24 of certain cavities 23 may each have an orifice 20 supply of gas.
- the characteristics of the cavities 23 and more generally of the reduction electrode 11 are the same as those described above.
- the device 30 comprises a container 31 intended to contain a deposition solution 5.
- the deposition solution 5 is an aqueous solution containing nickel in ionic form.
- This displacement or reduction process is particularly suitable for the deposition of a less noble metal than gold, such as for example copper or nickel, for thicknesses of about ten micrometers or for a deposit of gold whose desired thickness does not exceed about 1 to 2 micrometers.
- the device 30 comprises at least one reduction electrode 11, as described above.
- the body 12 and / or the head 13 of the electrode 11 are made of a non-metallic material.
- the object 1 is first introduced into the cavity 23 of the reduction electrode 11 by the orifice 28 provided for this purpose.
- This orifice 28 is then plugged by a plug 55, for example made of tetrafluoroethylene polymer so that the object 1 does not escape during the deposition.
- the reduction electrode 11 is immersed in the deposition solution 5.
- the oxidation-reduction reaction starts as soon as the object 1 is in contact with the deposition solution 5.
- the deposition solution 5 is stirred in order to set in motion and to keep the object 1 in suspension in the deposition solution 5.
- This stirring is carried out by stirring means 32.
- the stirring means 32 may, for "example, be an ultrasonic device 35 or a device 36,37 "typing" the reduction electrode 11. If the object 1 to be metallized was, for example, a microbead, stirring would, in addition to put in motion the deposition solution 5, maintain this microbead suspended in the cavity 23.
- the stirring will cause the object 1 to rise along the cavity 23 towards the surface of soil ution of 5.
- ⁇ 1 must be able to lower it so that it does not remain stationary in the cavity 23 and remains immersed.
- a gas is injected inside the cavity 23 intermittently.
- the injected gas is preferably a neutral gas such as nitrogen so as not to modify the pH of the deposition solution 5.
- the device 30 comprises gas injection means 38 connected to the gas supply port 20 of the head 13 of the reduction electrode 11.
- these means 38 are a capillary 39 connected to the gas supply port 20 and a peristaltic pump 40 for sending into the cavity 23 gas bubbles at a certain frequency.
- these means may be a capillary 39 connected to a gas circuit whose flow rate is regulated by a valve 41.
- the orifice 20 for supplying gas is located above the cavity 23 on the 3A, the gas bubbles will go down into the cavity 23, thus lowering the object 1, which then rises with the agitation of the solution 5.
- the frequency of sending the gas bubbles, parameterized on the pump 40 is preferably chosen such that the object 1 never stagnates in the upper part of the cavity 23. Typically, a gas bubble is sent into the cavity 23 every second.
- the agitation of the solution 5 also makes it possible to maintain the solution of homogeneous deposition and thus, also to maintain a sufficient electroactive species regeneration near the surface of the object 1.
- the metal of the object 1 oxidizes and releases electrons.
- the ions of the metal to be deposited in the deposition solution 5 are then reduced by these electrons on the object 1.
- the deposit solution contains in addition to the metal to be deposited, an additional metal in soluble ionic reduced form. This additional metal oxidizes and then generates the electrons necessary for the reduction of the metal to be deposited on the object 1.
- the solution 5 is preferably heated to a temperature of between about 60 0 C and 65 0 C.
- the device 30 comprises heating means 42.
- these heating means 42 are a heating plate located in the container 31, integrated with the stirring means 32.
- the device 30 may also comprise means for controlling the temperature of the solution 5.
- these means for controlling the temperature of the solution are an electronic thermometer 43 with a thermocouple 44, said thermocouple 44 being immersed in the deposit solution 5.
- Other ways of heating could have been envisaged such as a resistance to plunge into the deposition solution 5.
- the electrode 11 which is the subject of the present invention, is here a treatment electrode.
- This treatment electrode 11 is immersed in the solution 5 which is a solution "attacking" the material of the object 1 by oxidation-reduction reaction.
- the electrode will preferably be made at least partly based on an inert material to solution 5.
- other surface treatments of the object 1, metallic or not, other than chemical polishing such as degreasing, anodizing, phosphating or a. nitriding.
- the realization of these processes is identical to that of a chemical polishing.
- the nature of the treatment solution will be adapted according to the treatment of the desired object 1.
- the device 50 comprises a container 31 intended to contain a deposit solution 5.
- the deposition solution 5 is an aqueous solution based on potassium aurocyanide, thus containing gold in ionic form. Its chemical composition may for example be: - 25 grams of potassium aurocyanide per liter of solution,
- the pH of such a solution is about 4 to 5.
- the device 50 comprises at least one reduction electrode 11 as described above.
- the body 12 of the reduction electrode 11 is made of brass and is covered with an insulating coating such as a dielectric sheath 45 made of plastic, for example.
- the head 13 is made of brass and is covered with a layer of gold before depositing.
- the device 50 further comprises at least one electrode 46, called “oxidation electrode”, visible in FIG. 14.
- This electrode 46 is made based on a metal 47 that does not pollute the deposition solution 5, for example, for example , not in aluminum.
- the metal 47 is either insoluble, for example platinum, gold, stainless steel or titanium, or soluble. In the case of a soluble metal 47, it must be identical to the metal to be deposited, thus making it possible, by its oxidation, to regenerate the deposition solution 5 into metal ions, here gold.
- This electrode 46 may for example be formed of a single wire 47 which would be immersed in the deposition solution 5 during the deposition.
- the object 1 is first introduced into the cavity 23 of the reduction electrode 11 by the orifice 28 provided for this purpose. This orifice 28 is then closed by a plug 55, for example made of tetrafluoroethylene polymer so that the object 1 does not escape during the deposition.
- the oxidation electrode 46 and the reduction electrode 11 are then immersed in the deposition solution 5 contained in the container 31.
- the deposition solution 5 is stirred in order to set in motion and to keep the object 1 in suspension in the deposition solution 5.
- This agitation is carried out by means of agitation 32.
- FIG. 32 are an ultrasonic device 35.
- the advantage of this solution is that the ultrasound shake both the deposition solution 5 but also the object 1, which further improves the homogeneity of the deposit.
- a gas is injected inside the cavity 23.
- the injected gas is preferably a neutral gas.
- Gas injection means 38 comprise a capillary 39 connected to a gas circuit whose flow rate is regulated by a valve 41.
- the oxidation electrode 46 and the reduction electrode 11 are electrically connected to one another via a source of energy such as a current source 52.
- This current source 52 will circulate a current, here continuous, in the circuit thus formed and thus allow the deposition to be carried out on the object 1 by electrolysis.
- the current source can also deliver alternating current: it is called pulsed current deposition. In this case, the shape of the electrical signal is imposed and controlled. Then, successively and according to the sign of the current, a reduction or oxidation reaction on the surface of the object to be metallized, which may in certain cases improve the deposition.
- the deposition solution 5 is heated to a temperature of between approximately 60 ° C. and 65 ° C. by heating means 42.
- these heating means 42 are a heating plate located under the vessel 31, integrated in the stirring means 32.
- the device 50 may also comprise means for controlling the temperature of the deposition solution 5.
- these means for controlling the temperature of the the solution are for example an electronic thermometer 43 with thermocouple 44, said thermocouple 44 being immersed in the deposition solution 5.
- the device shown in FIG. 12 can also be used for carrying out an electrochemical polishing process, which is also an object of the present invention.
- the electrode 11, object of the present invention is an oxidation electrode.
- the geometry of this electrode 11 is identical to that described above, for example in connection with FIG. 3A.
- This electrode 11 is made of an electrically conductive material. Only the polarization of the electrode 11, here of oxidation, and the electrode 46, here of reduction, changes with respect to the electrolytic deposition, so that an oxidation reaction is carried out on the oxidation electrode 11 and on the object 1.
- the oxidation electrode 11 is connected to the negative pole at the current source 52. The oxidation which is carried out on the object 1 allows the polishing of this object 1 by removal of material.
- This method may for example be carried out for an electrochemical polishing of a tantalum microbead
- the oxidation electrode may for example be based on tantalum
- the reduction electrode is for example a platinum wire of 1 mm section. and a length of 5 mm.
- the device 60 comprises at least one container 31 containing at least one deposition solution 5.
- the deposition solution 5 is an aqueous solution based on aurocyanide. of potassium, thus containing gold in ionic form, identical to that of the example of electrolytic deposition process.
- This method is suitable for depositing all types of metals, whatever the desired thickness.
- the device 60 comprises at least one reduction electrode 11 similar to that used in the example of the electrolytic deposition process.
- the device 60 further comprises at least one oxidation electrode 46 visible in FIG. 14.
- This electrode 46 is made of a metal 47 having a reducing power greater than that which must be deposited, for example aluminum. , about 99.99% pure. It may for example be formed of a single wire 47 of aluminum which would be immersed in the deposition solution 5 during the deposition. But during the oxidation process of aluminum, the wire 47 would eventually be covered with gold, which would cause a drop in the deposition rate on the object 1.
- the electrode The conductive solution 49 is, for example, a solution filled with a conductive solution 49.
- This conductive solution 49 is, for example, a solution of saturated potassium chloride. An aluminum wire 47 is immersed in this conductive solution 4-9.
- the container 48 is closed by an ionic junction 51, here a glass frit.
- Ionic junction 51 may also be a gelatinous ionic junction.
- This ion junction 51 allows electrical contact between the deposition solution 5 and the conductive solution 49, while physically separating the two solutions 5, 49.
- the electrical migration between the two ionic solutions is ensured by the electric field created by a potential difference which is established between the electrode of In this way, no deposit of gold occurs on the aluminum 47, to ensure a constant rate of deposition on the object 1.
- FIG. 15 is a graph showing the intensity of the current flowing between the aluminum wire 47 and the object 1 when the aluminum wire
- curve 1 curve 1
- curve 2 shows that the electrical intensity remains substantially constant over time when the aluminum wire 47 is isolated from the deposition solution 5, which reflects a quasi-constant deposition rate.
- the object 1 is first introduced into the cavity 23 of the reduction electrode 11 by the orifice 28 provided for this purpose.
- This orifice 28 is then closed by a plug 55, for example made of tetrafluoroethylene polymer so that the object 1 does not escape during the deposition.
- the oxidation electrode 46 and the reduction electrode 11 are then immersed in the deposition solution 5 contained in the container 31.
- the deposition solution 5 is agitated in order to set in motion and to keep the object 1 in suspension in the deposition solution 5.
- This stirring is carried out by stirring means 32.
- a device 36, 37 "tap" the reduction electrode 11.
- This device consists of a piston 37 which comes to tap, at a frequency determined by a signal generator 36, the electrode of 11.
- a gas is injected into the cavity 23.
- the injected gas is preferably a neutral gas.
- Gas injection means 38 are a capillary 39 connected to a peristaltic pump 40.
- the oxidation electrode 46 and the reduction electrode 11 are electrically connected to each other. No energy source is needed in this type of process.
- This electrical connection will allow current to flow and therefore to deposit on the object 1 by stack effect when it is in contact with the wall 24 of the cavity 23 of the reduction electrode 11.
- This connection can be direct, or else be carried out via a coulometer 54, as in FIG. 13.
- FIG. 16 is a graph representing the deposition velocities, with (curve 3) and without coulometer 54 (curve 4).
- the advantage of the coulometer 54 with respect to a direct electrical connection is that it increases the internal resistance of the circuit. So, it increases the potential difference between the two electrodes 46 and 11.
- the resistance of the circuit is about 0.1 ohm for a potential difference close to 0 volts. Under these conditions, the deposition rate is about 4 micrometers per hour.
- the resistance of the circuit goes to 170 ohms, thus increasing the potential difference to 34 millivolts. The ionic migration through the ion junction 51 is then sufficient to guarantee a deposition rate of the order of 14 micrometers per hour.
- the deposition solution 5 is heated to a temperature of between approximately 60 ° C. and 65 ° C. by heating means 42.
- these heating means 42 are a
- the device 60 may also comprise means for controlling the temperature of the deposition solution 5.
- these means for controlling the temperature of the solution are an electronic thermometer 43 to thermocouple 44, said thermocouple 44 being immersed in the deposition solution 5.
- FIG. 17 represents the average speed of several deposits produced by the battery-effect chemical deposition method using a reduction electrode 11 according to the invention.
- the average speed obtained is 14.5 micrometers per hour plus or minus 3 micrometers per hour.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0550877A FR2883889B1 (fr) | 2005-04-04 | 2005-04-04 | Electrode de reduction pour depot de metal par oxydoreduction. |
PCT/FR2006/000732 WO2006106221A2 (fr) | 2005-04-04 | 2006-04-03 | Electrode de traitement de surface |
Publications (1)
Publication Number | Publication Date |
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EP1866462A2 true EP1866462A2 (fr) | 2007-12-19 |
Family
ID=34982441
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP06726175A Withdrawn EP1866462A2 (fr) | 2005-04-04 | 2006-04-03 | Electrode de traitement de surface |
Country Status (8)
Country | Link |
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US (1) | US8246797B2 (fr) |
EP (1) | EP1866462A2 (fr) |
JP (1) | JP5313661B2 (fr) |
CN (1) | CN101248220B (fr) |
AU (1) | AU2006231249B2 (fr) |
CA (1) | CA2603286C (fr) |
FR (1) | FR2883889B1 (fr) |
WO (1) | WO2006106221A2 (fr) |
Families Citing this family (4)
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CN103276376A (zh) * | 2013-06-14 | 2013-09-04 | 苏州异导光电材料科技有限公司 | 一种在高分子微球表面化学镀镍的方法 |
FR3008429A1 (fr) | 2013-07-12 | 2015-01-16 | Commissariat Energie Atomique | Procede de synthese d'une mousse metallique, mousse metallique, ses utilisations et dispositif comprenant une telle mousse metallique |
US10844507B2 (en) * | 2017-06-21 | 2020-11-24 | Lawrence Livermore National Security, Llc | Cathode system for electrodeposition of metals on microspheres |
CN117740883A (zh) * | 2023-12-19 | 2024-03-22 | 广东工业大学 | 一种用于管道堵塞的检测方法及装置 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR550877A (fr) | 1922-05-02 | 1923-03-22 | Sharples Specialty Co | Procédé pour la résolution des émulsions d'eau dans l'huile |
BR6913915D0 (pt) * | 1968-11-12 | 1973-01-02 | Wdylite Corp | Processo e aparelho para processamento de pecas a trabalhar |
US3664354A (en) * | 1968-11-12 | 1972-05-23 | Udylite Corp | Apparatus for processing workpieces |
CH555752A (de) * | 1972-06-02 | 1974-11-15 | Montblanc Simplo Gmbh | Kugelschreiberminenspitze. |
DE2543599A1 (de) * | 1975-09-30 | 1977-04-07 | Herbert Fruehschuetz | Vorrichtung zur elektrochemischen oberflaechenbehandlung von kleinteilen |
US4316786A (en) * | 1980-09-19 | 1982-02-23 | The United States Of America As Represented By The United States Department Of Energy | Apparatus for electroplating particles of small dimension |
JPS5881990A (ja) * | 1981-11-11 | 1983-05-17 | Fujitsu Ltd | 電気めつき処理方法 |
JPH04354881A (ja) * | 1991-05-31 | 1992-12-09 | Soken Kagaku Kk | 無電解鍍金方法 |
JPH08120497A (ja) * | 1994-10-21 | 1996-05-14 | Seikosha Co Ltd | 回転バレル装置 |
CN2270056Y (zh) * | 1996-06-14 | 1997-12-10 | 吕安 | 可移式电镀装置 |
US6174425B1 (en) * | 1997-05-14 | 2001-01-16 | Motorola, Inc. | Process for depositing a layer of material over a substrate |
-
2005
- 2005-04-04 FR FR0550877A patent/FR2883889B1/fr active Active
-
2006
- 2006-04-03 US US11/887,896 patent/US8246797B2/en active Active
- 2006-04-03 AU AU2006231249A patent/AU2006231249B2/en not_active Ceased
- 2006-04-03 WO PCT/FR2006/000732 patent/WO2006106221A2/fr active Application Filing
- 2006-04-03 EP EP06726175A patent/EP1866462A2/fr not_active Withdrawn
- 2006-04-03 CN CN200680018441.8A patent/CN101248220B/zh not_active Expired - Fee Related
- 2006-04-03 CA CA2603286A patent/CA2603286C/fr not_active Expired - Fee Related
- 2006-04-03 JP JP2008504803A patent/JP5313661B2/ja not_active Expired - Fee Related
Non-Patent Citations (1)
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None * |
Also Published As
Publication number | Publication date |
---|---|
CN101248220A (zh) | 2008-08-20 |
WO2006106221A3 (fr) | 2007-08-23 |
CN101248220B (zh) | 2011-02-09 |
US8246797B2 (en) | 2012-08-21 |
CA2603286A1 (fr) | 2006-10-12 |
WO2006106221A2 (fr) | 2006-10-12 |
US20090014321A1 (en) | 2009-01-15 |
JP5313661B2 (ja) | 2013-10-09 |
AU2006231249B2 (en) | 2012-02-02 |
FR2883889B1 (fr) | 2007-06-08 |
CA2603286C (fr) | 2014-03-25 |
AU2006231249A1 (en) | 2006-10-12 |
JP2008534787A (ja) | 2008-08-28 |
FR2883889A1 (fr) | 2006-10-06 |
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