WO2020084202A1 - Electrically conductive adhesive and (re)generation of (micro)electric circuits - Google Patents

Electrically conductive adhesive and (re)generation of (micro)electric circuits Download PDF

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Publication number
WO2020084202A1
WO2020084202A1 PCT/FR2019/000178 FR2019000178W WO2020084202A1 WO 2020084202 A1 WO2020084202 A1 WO 2020084202A1 FR 2019000178 W FR2019000178 W FR 2019000178W WO 2020084202 A1 WO2020084202 A1 WO 2020084202A1
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WO
WIPO (PCT)
Prior art keywords
electrically conductive
conductive adhesive
composition
electrical
pigment
Prior art date
Application number
PCT/FR2019/000178
Other languages
French (fr)
Inventor
Thomas SOUVIGNET
David Naccache
Thibaut HECKMANN
Original Assignee
L'etat Français Représenté Par Le Ministère De L'intérieur
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Publication of WO2020084202A1 publication Critical patent/WO2020084202A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the present invention relates to a method of micro-bonding of bonding wires using an ablation laser, as well as the various means of implementing this method such as the various compositions of electrically conductive adhesives developed in this context and usable in microelectronics.
  • the "wire bonder” is unusable in areas where the density of links is too high.
  • the “wire bonder” cannot be used to repair the links located in the memory area or in the processor area.
  • the risk of destruction of neighboring links is very high and the benefit / risk ratio of repair using this traditional technique is very low. Indeed, making a repair of the connecting wire by applying electrically conductive glue to the place of destruction is made impossible in front of the density of wires. The creation of false contacts between two neighboring connecting wires is systematic.
  • the Applicant has used a laser beam in order to vaporize the residues of conductive adhesives located between the connections which create the short circuits.
  • a laser overpower of the order of 60% of the maximum power 30W
  • the electronic components detruction of data, risk of touch silicon, etc.
  • the Applicant had the idea of adding an additive to the glue in order to make it more volatile to laser radiation.
  • the additive it is possible to use a laser beam in order to vaporize the residues of conductive adhesives at powers of the order of 45% of the maximum power 30W, which do not damage the electronic circuits. or their components.
  • the object of the present invention therefore relates to an electrically conductive adhesive composition, characterized in that it comprises:
  • the object of the present invention therefore also relates to the process for the manufacture of an electrically conductive adhesive composition as presently described, comprising the following successive steps:
  • step (b1) adding to the container of step (a1) at least one pigment and / or at least one dye sensitive to laser radiation,
  • step (d1) recovery of the composition obtained in step (c1).
  • the object of the present invention further relates to the use of an electrically conductive adhesive composition according to the present invention for the construction or reconstruction of electrical circuits.
  • the object of the present invention further relates to the method of selecting a dye or a pigment sensitive to laser radiation (for the implementation of the glue manufacturing process, and / or the construction or reconstruction method or method according to the invention) characterized by the following successive steps:
  • step (b2) collection or production of an absorption spectrum of the dye or pigment preselected in step (a2);
  • step (c2) selection of the wavelength of the laser radiation to be used as a function of the spectrum obtained in step (b2).
  • the object of the present invention also relates to the method of construction or reconstruction of an electrical circuit, preferably electronic or microelectronic, characterized by the following successive steps:
  • step (b3) optionally, treatment of the composition of electrically conductive adhesive of step (a3) so that this composition freezes
  • step (c3) applying laser radiation to the areas to be removed from the electrical conductive composition deposited in step (a3) in order to build or reconstruct a desired conductive portion;
  • the object of the present invention thus relates to a device for creating electrical conductive links comprising a laser suitable for the implementation of the method of construction or reconstruction of an electrical circuit as described herein.
  • the object of the present invention therefore relates to an electric, electronic or microelectronic circuit comprising an electrically conductive adhesive composition according to the present invention.
  • the object of the present invention further relates to an electrical or electronic device comprising at least one electrical, electronic or microelectronic circuit comprising an electrically conductive adhesive composition according to the present invention.
  • matrix of electrically conductive adhesive it is understood in the context of the present invention a substance constituting the matrix, electrically conductive, making it possible to make electrical contacts, while ensuring adhesion to the substrate to which it is applied. .
  • it is the adhesive matrix which essentially allows the adhesive properties of the adhesive composition "matrix + pigment".
  • the substrate on which the glue is applied may be more or less sensitive to temperature, which justifies the use of a matrix, the implementation of which avoids temperatures which can alter said substrate.
  • the matrices of electrically conductive adhesives which are typically of a polymeric nature such as a resin, are generally much more flexible than conventional welds, which allows them to better resist vibrations or external shocks.
  • ICA glue is electrically conductive in all directions. ICA glue is used for applications such as contact chip bonding and SMD component bonding. ACA glue contains specific conductive particles, which conduct electricity in one direction. This adhesive is used in many sensitive structures on circuits, such as for bonding RFID antenna structures, LCD connections or flexible PCBs.
  • Conductive adhesives typically have a viscosity of between one to several hundred mPas (for example 200 mPas) up to several tens of thousands of mPas (for example 50,000 mPas ).
  • the adhesives used preferably have a viscosity of between 2000 and 15000 mPas.
  • any known chemical nature of electrically conductive adhesives is applicable to the subject of the present invention.
  • the adhesives can thus be, for example, epoxy, polyimide, acrylate, polyester adhesives, etc. sensitive or not to UV radiation. If it is possible that metal compounds may be present in the matrix of these adhesives, a high concentration of these metal compounds is not desirable in the context of the present invention: it would then be more difficult (if not impossible) to remove these metals by a laser application without altering the substrate.
  • the matrices of conductive adhesives on the market typically contain metals at concentrations allowing the implementation of the present invention without altering the substrate. Thus, the presence of these metallic compounds not being obligatory as for the implementation of the present invention, it is left to the skilled person the appreciation of their additions in the adhesives of the present invention in order to obtain desired additional effects.
  • the adhesive / matrix can be fixed or not.
  • the adhesive matrix can be more or less organized, more or less flexible, more or less fixed.
  • pigment and / or dye sensitive to laser radiation any chemical entity whose entropy will increase when said pigment and / or dye is subjected to one or more radiation (s) laser (s). It is implicit in the context of the present invention that the pigment / dye is added at a concentration that does not block the conductivity of the adhesive, or in the desired amount so as not to block the adhesion properties of the adhesive.
  • construction or reconstruction of electrical circuits it is understood in the context of the present invention to create electrical conductive connections between at least two points allowing an exchange of electricity (ie on an electrical circuit). If this / these links previously existed, it will be a reconstruction (ie a repair), if it is the creation of a new link, then we will speak of construction.
  • electrical circuit it is understood in the context of the present invention at least one physical link, preferably a network of physical links, allowing the exchange of electricity.
  • a physical link preferably a network of physical links, allowing the exchange of electricity.
  • a microelectronic circuit is an electronic circuit which includes physical electrical connections allowing the exchange of electricity, which connections are of micrometric size (ie between 1 and 1000 ⁇ m, preferably less than 1000 ⁇ m, 500 pm, 250 pm, 100 pm, 50 pm, 10 pm, 5 pm or even less than 3 pm).
  • electrical conductive links is meant wires of nanometric diameter (between 1 and 10 nm) and micrometric diameter (between 1 and 1000 pm, preferably less than 1000 pm, 500 pm, 250 pm, 100 pm, 50 pm, 10 pm, 5 pm or even less than 3 pm).
  • composition of conductive adhesive The electrically conductive adhesive composition according to the present invention can be characterized in that its matrix is suitable for its use in electronics and / or in microelectronics.
  • the advantage of the present invention is that the composition of electrically conductive adhesive can be a conventional industrial electrically conductive adhesive (without pigment) constituting the matrix, to which the pigment and / or dye according to the present invention is added.
  • composition of electrically conductive adhesive according to the present invention can be characterized in that the matrix is an adhesive as defined above (cf. Definitions) and can for example be polymeric (epoxy, polyimides, acrylates, polyester, etc.).
  • the composition of electrically conductive adhesive according to the present invention can be characterized in that the matrix is an electrically conductive adhesive chosen from the list consisting of epoxy adhesives, silicones, polyurethanes, polyimides, acrylates.
  • the polymerization of these adhesives can be carried out by the application of a temperature variation (eg heating) or the use of a catalyst.
  • the composition of electrically conductive adhesive according to the present invention can be polymerized by applying a temperature above 95 ° C. for a time between a few seconds and 1 hour, for example between 1 to 10 minutes.
  • epoxy adhesives for example, can be 1 or 2 components according to the usual ratios of the art (typically 1 to 1 by mass).
  • the electrically conductive adhesive composition according to the present invention can be further characterized in that it is free from solvents.
  • An electrically conductive adhesive used in the context of the present invention as a matrix can be Polytec EC15IL® (epoxy base), Polytec EC151 L-frozen® (epoxy), Polytec EC101® (epoxy base), Polytec EC101- L-frozen® ( epoxy), Polytec EC1 12L-frozen® (epoxy), Polytec EC201® (epoxy), Polytec EC242-frozen® (epoxy), Polytec EC262-2® (epoxy), Polytec PU-1000® (polyurethane), Polytec SB1227® (epoxy), Electrolube Silver Conductive Adhesive Paint®, RS Pro Silver Conductive Adhesive Paint ®, RS Pro Silver Conductive Adhesive Paint, RS Pro Silver Conductive Adhesive Epoxy®, Chemtronics Silver Conductive Adhesive Epoxy®, MG Chemicals Silver
  • the electrical conductive adhesives according to the present invention can be adapted to adhesion to metals (ferrous or non-ferrous metals), glasses, ceramics, and / or plastics. Conventionally, the supports are cleaned before application of the composition (s) of electrically conductive adhesive (s) according to the present invention.
  • the electrical conductive adhesives according to the present invention can be adapted to flexible electrical circuits or to substrates insensitive to external physical stress factors (i.e. support having sufficient rigidity).
  • the electrically conductive adhesives which can be used according to the present invention are suitable for the connection of ceramic fuses, for the printing of antennas for the binding of all types of components, more particularly to the binding of components sensitive to heat, to the connection of flexible components, to the connection of flexible circuits, to the flexible printed conductors on flexible support and / or to screen printing.
  • Electrically conductive adhesives may contain one or more agents allowing the passage of electric current, such as metal atoms and / or ions, and / or conductive particles.
  • the electrically conductive adhesives according to the present invention can contain graphite, silver, iron, nickel, zinc, copper, organic and / or mineral salts.
  • An example of an electrically conductive adhesive which can be used according to the invention may comprise the following compounds: N-butyl acetate, silver, 2-butoxyethyl acetate, 2-methoxy-1-methylethyl acetate, 3,6-diazaoctanethylenediamine.
  • an electrically conductive adhesive which can be used according to the invention can comprise the following compounds: alkyl ether (C1 to C8) glycidyl, aluminum oxide, bisphenol-A, epoxy resin, carbon black, phenol epoxy, novalaque resin, diglycidyl ether neopentyl glycol, zinc oxide.
  • composition of electrically conductive adhesive usable as a matrix according to the present invention can be characterized in that it has a viscosity at 23 ° C. between 500 and 50,000 mPa.s before polymerization, for example less than 45,000 mPa.s, less than 25,000 mPa.s, less than 10,000 mPa.s, less than 6,000 mPa.s, preferably less than 5,000 mPa.s.
  • the composition of electrically conductive adhesive according to the present invention can be characterized in that the matrix has a viscosity at 23 ° C. before polymerization of between 1000 and 45000 mPa.s, between 2000 and 25000 mPa.s, between 3000 and 10,000 mPa.s, preferably between 4,000 and 8,000 mPa.s.
  • the electrically conductive adhesive composition according to the present invention can be characterized in that said pigment and / or dye absorbs at a wavelength between 500 nm and 1100 nm, preferably between 532 nm and 1064 nm.
  • the wavelength is between 500 and 600 nm, preferably between 510 and 550 nm, more preferably between 520 and 540 nm, even more preferably between 530 and 535 nm, such as 532 nm.
  • the wavelength is between 1000 and 1100 nm, preferably between 1040 and 1090 nm, more preferably between 1050 and 1080 nm, even more preferably between 1060 and 1070 nm, such as 1064 nm.
  • composition of electrically conductive adhesive according to the present invention can be characterized in that said pigment and / or dye is chosen from Indigo, Erichrome Black T and Sudan Black.
  • said pigment and / or dye is chosen from Indigo and Erichrome Black T for their property of electrical conductivity. More advantageously, said pigment and / or dye is Erichrome Black T for its homogeneous incorporation in conductive adhesives.
  • the composition of electrically conductive glue according to the present invention can be characterized in that the amount of said dye and / or pigment makes it possible to obtain a resistance of the composition of electrically conductive glue once frozen capable of allowing an electrical connection during at least an hour.
  • the composition of electrically conductive adhesive according to the present invention allows an electrical connection for at least 6 hours. More preferably, once the composition of electrically conductive adhesive according to the present invention has been fixed, it allows an electrical connection for at least 24 hours, at least a week at least a month. Even more preferably, once the composition of electrically conductive adhesive according to the present invention has been fixed, it allows an electrical connection for at least one year.
  • the object of the present invention therefore relates to an electrically conductive adhesive composition for the creation or reconstruction of electrical circuits, preferably electronic and / or microelectronic circuits.
  • the subject of the present invention relates to a method of creating or reconstructing electrical circuits, preferably electronic and / or microelectronic circuits involving the use of an electrically conductive adhesive composition according to the present invention.
  • composition of electrically conductive adhesive according to the present invention can be characterized in that the electrical circuit comes from or is intended for a fixed electronic device, such as a desktop computer or a computer server, or a portable electronic device, such as a mobile phone, a smart phone, a computer tablet, a laptop, a GPS, a camcorder, a camera, a dictaphone, an on-board camera, a computer on board a vehicle, an on-board recorder in a vehicle.
  • a fixed electronic device such as a desktop computer or a computer server
  • a portable electronic device such as a mobile phone, a smart phone, a computer tablet, a laptop, a GPS, a camcorder, a camera, a dictaphone, an on-board camera, a computer on board a vehicle, an on-board recorder in a vehicle.
  • composition of electrically conductive adhesive according to the present invention can be characterized in that the electrical circuit is or comes from a computer motherboard, a computer video card, a computer memory such as a hard disk. SSD, an SD or micro SD card or a flash card, a processor, a ram module, a SIM card.
  • the object of the present invention thus also relates to the process for the manufacture of an electrically conductive adhesive composition as defined above.
  • the process for manufacturing the composition of electrically conductive adhesive according to the invention is carried out industrially, ie automated.
  • the process for manufacturing the composition of electrically conductive adhesive according to the invention is carried out on a case-by-case basis, on the scale of milliliter (between 0.5 ml_ and 500 ml), or on a liter scale (between 0.5 L and 50 L) and can therefore be carried out by a single preparer.
  • step (b1) when there are several additions of pigment (s) and / or dye (s) in step (b1), these additions are made simultaneously (reduction in the number of steps of the process).
  • the addition of these pigment (s) and / or dye (s) can be carried out successively if there is an advantage in doing so, for example in terms of the solubility of the pigment (s) and / or dye (s) in the conductive glue matrix.
  • Step (c1) of mixing the composition obtained in step (b1) is carried out so that all of the pigment (s) and / or dye (s) are distributed uniformly in the matrix of conductive glue.
  • Step (d1) of recovery of the composition obtained in step (c1) is carried out by any suitable manner known in the art in view of the quantities involved.
  • a packaging step in a container intended for sale and / or transport can be added to step (d1).
  • the object of the present invention thus also relates to the method of selecting a dye or a pigment sensitive to laser radiation (for the implementation of the glue manufacturing process, and / or the construction or reconstruction method or method according to the invention), as defined above.
  • step (a2) of preselecting a dye, a pigment or a mixture thereof is done using bibliographic data (such as a supplier catalog) known on pigments, dyes or a mixture thereof.
  • This preselection can be conditioned by a laser apparatus (and therefore the wavelengths already preselected) already in use for possibly other applications, or quite simply for questions of purchase price of the pigments, dyes or of a mixture. of these.
  • Step (b2) of collecting or producing an absorption spectrum of the dye or pigment preselected in step (a2) is carried out by consulting the known bibliographic data (“collection”) of the dye or pigment preselected in step (a2), or of a conventional technique in the art of absorption spectrometric analysis.
  • This selection step can be a refinement of the wavelength of the device already in the possession of the user, if possible.
  • Another way of carrying out the invention is to preselect several dyes, pigments and / or mixtures thereof, to collect for each samples the absorption wavelengths, then to select the sample (s) having the best absorptions at a predefined wavelength (in the case where one is already in possession of the laser material).
  • the method of selecting a dye or a pigment sensitive to laser radiation can be characterized in that the step (c2) of selecting the wavelength of the laser radiation is carried out for a wavelength representing one of the 10 most intense peaks of the absorption spectrum obtained in step (b2).
  • the method of selecting a dye or a pigment sensitive to laser radiation can be characterized in that it comprises an additional step (d2) of determining the power of the laser radiation selected in step (c2), making it possible to keep the integrity of the electronic component at build or reconstruct, characterized in that step (d2) is an exposure to different powers of the laser radiation selected in step (c2) of a support of the same nature as the support of the electronic component to be built or to reconstruct , and to choose a power lower than that altering the surface of the support for a given treatment time.
  • a step (e2) of testing the conductivity of a fixed adhesive according to the present invention comprising the dye and / or pigment selected to ensure that this mixture can be used in electronics.
  • the object of the present invention also relates to the method of construction or reconstruction of an electrical circuit, preferably electronic or microelectronic, as defined above.
  • step (a3) of depositing composition of electrically conductive adhesive according to the present invention on a desired area of an electrical circuit or of a support for an electrical circuit is carried out by means of suitable equipment. the size of said electrical circuit.
  • This step can also be carried out via visual or video control using a microscope.
  • the optional step (b3) of treatment of the composition of electrically conductive adhesive of step (a3) so that this frozen composition can be carried out by suitable heating, by electromagnetic radiation such as 'an application of UV radiation, and / or a vacuum.
  • step (c3) of applying laser radiation to the areas to be removed from the electrically conductive composition deposited in step (a3) in order to build or reconstruct a desired conductive portion is carried out using an ablation laser, pulsed or not, for example of the “Ytterbium doped Fiber®” type at 1064 nm.
  • the power of the laser can be less than 30W, 25W, 20W, 15W, 10W or even less than 5W.
  • the laser power is between 5W and 30W, preferably between 10W and 20W, for example 15W ⁇ 3 W.
  • the contact surface of the laser applied is less than 1 mm 2 , less than 1000 pm 2 , less than 100 pm 2 , less than 10 pm 2 , less than 1 pm 2 , or even less than 0.1 pm 2 .
  • the ratio between the power of the applied laser and the contact surface of said laser is less than 1 W / pm 2 , less than 0.5 W / pm 2 , less than 0.3 W / pm 2 , less than 0.25 W / pm 2 , less than 0.2 W / pm 2 , less than 0.15 W / pm 2 , less than 0.1 W / pm 2 , or even less than 0.05W / pm 2 .
  • step (c3) of applying laser radiation to the areas to be removed from the electrically conductive composition deposited in step (a3) can be characterized in that the treatment time allows spray all the glue subjected to laser radiation.
  • step (d3) of recovery of the electrical circuit thus treated is carried out without additional treatment.
  • the electrical circuit can be washed with a suitable solvent, such as with deionized water, or blowing with air or a neutral gas, in order to remove any waste from the treatment of the step (c3).
  • the object of the present invention also relates to the device for creating electrical conductive links comprising a laser suitable for implementing the method of construction or reconstruction of an electric circuit as described herein.
  • the device according to the present invention comprises a laser suitable for implementing the method of construction or reconstruction of an electrical circuit according to the present invention.
  • the device according to the present invention can be characterized in that said device is a device for micrometric implementation.
  • Electric circuit comprising a conductive adhesive composition
  • the object of the present invention also relates to an electrical, electronic or microelectronic circuit comprising an electrically conductive adhesive composition (which may or may not be fixed), as described herein.
  • the subject of the present invention thus relates to the electrical, electronic or microelectronic circuit comprising an electrically conductive adhesive composition capable of being obtained by the method as described herein.
  • FIGURES Photograph of a shot using an electron microscope of access to the silicon memory after two physical attacks (laser). Degradation of several connecting wires can be observed.
  • FIG. 2 Figure 2A, 2B: Photographs of shots taken using a scanning electron microscope of connecting wires partially destroyed during physical attacks.
  • Figure 2C Enlargement of an electron microscope photograph of connection wires partially destroyed during a physical attack. Degradation of several connecting wires can be observed.
  • FIG. 3 Graph showing the measurement of the average depth removed (average over 5 measurements) by the application of a laser on a conductive industrial adhesive free of dye or pigment (measurement taken using a focal plane microscope).
  • the laser vaporizes the industrial conductive glue but from a power of 60% of the maximum laser power (30W).
  • the problem is that with such power, the laser irreversibly damages the electronic component (destruction of the data, risk of touching the silicon).
  • FIG.5 Figure 5A: Graph showing the measurement using a focal plane microscope of the average depth removed (average over 2 measurements) by the application of a laser on an industrial conductive adhesive containing indigo 0% by mass (lowest curve - control); 8.8% by mass (intermediate height curve) and 25% by mass (highest curve). It can be seen that the curves for 8.5% and 25% are relatively close.
  • Figure 5B Graph showing the measurement using a focal plane microscope of the average depth removed (average over 2 measurements) by the application of a laser on a conductive industrial adhesive containing “Erichrome Black T” at a height of 0% mass (lowest curve - control); 12% by mass (second curve from the bottom), 36% by mass (third curve from the bottom) and 60% by mass (fourth curve from the bottom). It can be seen that the third and fourth curves for 36% and 60% are almost juxtaposed.
  • FIG. 6 Figure 6 A: Representation of the spatial intensity of a laser beam along the plane (X, Y) perpendicular to the axis of propagation. The center of the beam is where the greatest energy (Emax) is measured (thus ensuring the precision of the treatment when applying the laser).
  • Emax the greatest energy
  • w represents the distance difference between Emax and 0.135 Emax. It corresponds to the radius of the laser beam taken at 0.135 (inverse of Néper's irrational constant squared) of the maximum irradiance.
  • the acronym “e” represents the irrational constant of Neper equal to 2.71,828.
  • Figure 6B Representation of the spatial intensity of the laser beam along the z axis perpendicular to the propagation axis.
  • the acronym “Wo” represents the radius of the laser beam at the point "waist”.
  • the acronym “R (z)” represents the module in cylindrical coordinates, the acronym “Q” represents the azimuth in cylindrical coordinates and the acronym “z” represents the dimension in cylindrical coordinates.
  • the acronym “ZR” represents the Rayleigh constant.
  • the point “V2Wo” represents the radius of the laser beam taken at the Rayleigh distance from the “waist”.
  • FIG. 7 Photographs of shots taken with an electron microscope at different stages of the process according to the invention.
  • FIG. 7A represents a broken connecting wire before treatment.
  • FIG. 7B represents the first step of applying the glue from the present invention to the portion of the photograph in FIG. 7A.
  • FIG. 7D represents the portion of the photograph in FIG. 7A repaired with a conductive micro-bonding of 15m micro-meter produced by laser attack. The electrical passage is ensured in case 7D, which made it possible to read the information contained on the damaged part.
  • the adhesive used in the context of the present invention is "polytec EC151 L®" which is a solid adhesive with two components, electrically conductive, epoxy type. Its observed viscosity is 4800 mPa.s. Its lifespan at room temperature observed is 2 days. At a temperature of 60 ° C for 90 minutes, sufficient setting (polymerization) was observed. A treatment at 150 ° C for 15 minutes or at 180 ° C for 40 seconds are also applicable for its polymerization depending on the case. The indicated thermal degradation temperature is 400 ° C with intermediate temperatures (without degradations) between -55 ° C and 300 ° C. The particular chemistry of epoxy adhesives allows rapid polymerization at a high temperature (ie above 100 ° C) and allows to be stressed (keep its physicochemical properties) also at high temperatures (up to 300 ° C, or even 400 ° C).
  • the laser used in the context of the present invention is an "Nd: Yag ®" laser, with a power of 30 W, adjustable, operating in the context of the present invention at 1064nm (or even 532 nm depending on the case of species).
  • titanium dioxide which does not absorb at 1064nm (wavelength used) was not used for the rest of the study.
  • Example 1 Determination of adhesives comprising dyes / pigments
  • Example 2 Method for reconstructing a microelectronic circuit
  • FIG. 7C A mask defining the path where to apply the laser has been defined (FIG. 7C).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

The invention relates to a method for manufacturing or constructing or reconstructing electric circuits, in particular on the micrometric scale, as well as the means for implementing such a method such as the use and manufacture of an electrically conductive adhesive, by means of laser ablation.

Description

Colle conductrice électrique et (ré)génération de circuits  Electrically conductive adhesive and (re) generation of circuits
(micro)électriques|  (micro) electric |
[0001] [La présente invention concerne un procédé de micro-collage de fils de liaisons utilisant un laser d’ablation, ainsi que les différents moyens de mise en oeuvre de ce procédé tels que les différentes compositions de colles conductrices électriques mises au point dans ce contexte et utilisables en microélectroniques.  [0001] The present invention relates to a method of micro-bonding of bonding wires using an ablation laser, as well as the various means of implementing this method such as the various compositions of electrically conductive adhesives developed in this context and usable in microelectronics.
[0002] La récupération de données sensibles dans les appareils électriques dépend de l’état des connexions, encore appelées liaisons, entre et dans les différents composants électroniques contenus dans ces appareils. Ces données binaires représentent en réalité les données utilisateurs (SMS, MMS, courriels, photos, vidéos, journal des appels, etc.). The recovery of sensitive data in electrical devices depends on the state of the connections, also called links, between and in the various electronic components contained in these devices. This binary data actually represents user data (SMS, MMS, emails, photos, videos, call log, etc.).
[0003] Pour atteindre le silicium, les experts/enquêteurs doivent souvent réaliser une attaque physique afin de retirer la partie isolante du composant électronique endommagé. Lors de ces attaques physiques, la destruction des fils de liaison (câbles électriques de 15 micromètres de diamètre) qui sont soudés sur le silicium et sont reliés aux couches internes en cuivres du composant est quasi systématique. La destruction des fils de liaison peut également arriver à la suite d’un choc sur le composant électronique (destruction volontaire, crash aérien, accident...). Cette destruction traduit l’impossibilité de récupérer les données ou les clés de chiffrement. To reach silicon, experts / investigators must often carry out a physical attack in order to remove the insulating part from the damaged electronic component. During these physical attacks, the destruction of the connecting wires (electrical cables of 15 micrometers in diameter) which are soldered to the silicon and are connected to the internal copper layers of the component is almost systematic. The destruction of the connecting wires can also happen following a shock on the electronic component (deliberate destruction, air crash, accident ...). This destruction indicates the impossibility of recovering the data or the encryption keys.
[0004] Dans les réalisations antérieures, la réparation de fils de liaison est réalisée en récréant l’intégralité des fils détruits par un dispositif communément appelé dans l’art « wire bonder ». Par exemple le document US 7227095B2 illustre cet état de la technique. In previous embodiments, the repair of connecting wires is carried out by recreating all of the wires destroyed by a device commonly called in the art "wire bonder". For example, document US 7227095B2 illustrates this state of the art.
[0005] Toutefois, le « wire bonder » est inutilisable dans les zones où la densité de liaisons est trop importante. Typiquement, le « wire bonder » n’est pas utilisable pour réparer les liaisons se trouvant dans la zone mémoire ni dans la zone processeur. Le risque de destruction des liaisons voisines est très important et le ratio bénéfice/risque de la réparation par cette technique traditionnelle est très faible. En effet, réaliser une réparation du fil de liaison en appliquant de la colle conductrice électrique à l’endroit de la destruction est rendue impossible devant la densité de fils. La création de faux contacts entre deux fils de liaison voisins est systématique. However, the "wire bonder" is unusable in areas where the density of links is too high. Typically, the "wire bonder" cannot be used to repair the links located in the memory area or in the processor area. The risk of destruction of neighboring links is very high and the benefit / risk ratio of repair using this traditional technique is very low. Indeed, making a repair of the connecting wire by applying electrically conductive glue to the place of destruction is made impossible in front of the density of wires. The creation of false contacts between two neighboring connecting wires is systematic.
[0006] Afin de surmonter ce problème, la Demanderesse a utilisé un faisceau laser afin de vaporiser les résidus de colles conductrices se trouvant entre les liaisons qui créent les courts circuits. Toutefois, utiliser des colles conductrices classiques oblige l’application d’une surpuissance du laser (de l’ordre de 60% de la puissance maximale 30W), ce qui altère de manière définitive et irrémédiable les composants électroniques (destruction de données, risque de toucher le silicium, etc.). In order to overcome this problem, the Applicant has used a laser beam in order to vaporize the residues of conductive adhesives located between the connections which create the short circuits. However, using conventional conductive adhesives requires the application of a laser overpower (of the order of 60% of the maximum power 30W), which permanently and irreparably alters the electronic components (destruction of data, risk of touch silicon, etc.).
[0007] Afin de remédier à ce problème, la Demanderesse a eu l’idée d’ajouter un additif dans la colle afin de la rendre plus volatile au rayonnement laser. Ainsi, après une sélection de l’additif, il est possible d’utiliser un faisceau laser afin de vaporiser les résidus de colles conductrices à des puissances de l’ordre de 45% de la puissance maximale 30W, qui ne détériorent pas les circuits électroniques ou leurs composants. In order to remedy this problem, the Applicant had the idea of adding an additive to the glue in order to make it more volatile to laser radiation. Thus, after selecting the additive, it is possible to use a laser beam in order to vaporize the residues of conductive adhesives at powers of the order of 45% of the maximum power 30W, which do not damage the electronic circuits. or their components.
[0008] RESUME DE L’INVENTION SUMMARY OF THE INVENTION
[0009] L’objet de la présente invention concerne donc une composition de colle conductrice électrique caractérisée en ce qu’elle comprend : The object of the present invention therefore relates to an electrically conductive adhesive composition, characterized in that it comprises:
- une matrice de colle conductrice électrique, - a matrix of electrically conductive adhesive,
- au moins un pigment et/ou au moins un colorant sensible à un rayonnement laser. - at least one pigment and / or at least one dye sensitive to laser radiation.
[0010] L’objet de la présente invention concerne donc également le procédé de fabrication d’une composition de colle conductrice électrique telle que présentement décrite, comprenant les étapes successives suivantes : The object of the present invention therefore also relates to the process for the manufacture of an electrically conductive adhesive composition as presently described, comprising the following successive steps:
(a1 ) ajout dans un récipient d’une matrice de colle conductrice électrique, (a1) addition of an electrically conductive glue matrix to a container,
(b1 ) ajout dans le récipient de l’étape (a1 ) d’au moins un pigment et/ou d’au moins un colorant sensible à un rayonnement laser, (b1) adding to the container of step (a1) at least one pigment and / or at least one dye sensitive to laser radiation,
(c1 ) mélange de la composition obtenue à l’étape (b1 ) , et (c1) mixing the composition obtained in step (b1), and
(d1 ) récupération de la composition obtenue à l’étape (c1 ). [0011] L’objet de la présente invention concerne en outre l’utilisation d’une composition de colle conductrice électrique selon la présente invention pour la construction ou la reconstruction de circuits électriques. (d1) recovery of the composition obtained in step (c1). The object of the present invention further relates to the use of an electrically conductive adhesive composition according to the present invention for the construction or reconstruction of electrical circuits.
[0012] L’objet de la présente invention concerne de plus le procédé de sélection d’un colorant ou d’un pigment sensible à un rayonnement laser (pour la mise en œuvre du procédé de fabrication de la colle, et/ou de la méthode ou du procédé de construction ou reconstruction selon l’invention) caractérisé par les étapes successives suivantes : The object of the present invention further relates to the method of selecting a dye or a pigment sensitive to laser radiation (for the implementation of the glue manufacturing process, and / or the construction or reconstruction method or method according to the invention) characterized by the following successive steps:
(a2) présélection d’un colorant, d’un pigment ou d’un mélange de ceux-ci, (a2) preselection of a dye, a pigment or a mixture thereof,
(b2) recueil ou réalisation d’un spectre d’absorption du colorant ou pigment présélectionné à l’étape (a2) ; et (b2) collection or production of an absorption spectrum of the dye or pigment preselected in step (a2); and
(c2) sélection de la longueur d’onde du rayonnement laser à utiliser en fonction du spectre obtenu à l’étape (b2). (c2) selection of the wavelength of the laser radiation to be used as a function of the spectrum obtained in step (b2).
[0013] L’objet de la présente invention concerne également le procédé de construction ou reconstruction d’un circuit électrique, préférentiellement électronique ou microélectronique, caractérisé par les étapes successives suivantes :  The object of the present invention also relates to the method of construction or reconstruction of an electrical circuit, preferably electronic or microelectronic, characterized by the following successive steps:
(a3) dépôt de composition de colle conductrice électrique selon la présente invention sur une zone souhaitée d’un circuit électrique ou d’un support pour circuit électrique, (a3) depositing an electrically conductive adhesive composition according to the present invention on a desired area of an electrical circuit or of a support for an electrical circuit,
(b3) optionnellement, traitement de la composition de colle conductrice électrique de l’étape (a3) pour que cette composition fige,  (b3) optionally, treatment of the composition of electrically conductive adhesive of step (a3) so that this composition freezes,
(c3) application d’un rayonnement laser sur les zones à retirer de la composition conductrice électrique déposée à l’étape (a3) afin de construire ou reconstruire une portion conductrice voulue ; et (c3) applying laser radiation to the areas to be removed from the electrical conductive composition deposited in step (a3) in order to build or reconstruct a desired conductive portion; and
(d3) récupération du circuit électrique ainsi traité. (d3) recovery of the electrical circuit thus treated.
[0014] L’objet de la présente invention concerne ainsi un dispositif de création de liens conducteurs électriques comprenant un laser adapté à la mise en œuvre du procédé de construction ou reconstruction d’un circuit électrique tel que décrit présentement. [0015] L’objet de la présente invention concerne donc un circuit électrique, électronique ou microélectronique comprenant une composition de colle conductrice électrique selon la présente invention. The object of the present invention thus relates to a device for creating electrical conductive links comprising a laser suitable for the implementation of the method of construction or reconstruction of an electrical circuit as described herein. The object of the present invention therefore relates to an electric, electronic or microelectronic circuit comprising an electrically conductive adhesive composition according to the present invention.
[0016] L’objet de la présente invention concerne par ailleurs un appareil électrique ou électronique comprenant au moins un circuit électrique, électronique ou microélectronique comprenant une composition de colle conductrice électrique selon la présente invention. The object of the present invention further relates to an electrical or electronic device comprising at least one electrical, electronic or microelectronic circuit comprising an electrically conductive adhesive composition according to the present invention.
[0017] DEFINITIONS DEFINITIONS
[0018] Par « matrice de colle conductrice électrique », il est compris dans le contexte de la présente invention une substance constituant la matrice, conductrice électriquement, permettant de faire des contacts électriques, tout en assurant une adhésion au substrat à laquelle elle est appliquée. Dans la présente invention, c’est la matrice de colle qui permet essentiellement les propriétés adhésives de la composition de colle « matrice + pigment ». Le substrat sur lequel est appliquée la colle peut être plus ou moins sensible à la température, ce qui justifie l’utilisation d’une matrice dont la mise en œuvre évite les températures pouvant altérer ledit substrat. De plus, les matrices de colles conductrices électriques, qui sont typiquement de nature polymérique telle qu’une résine, sont généralement beaucoup plus souples que des soudures classiques, ce qui leur permet de mieux résister aux vibrations ou aux chocs externes. Il existe deux types de colles conductrices d'électricité : les colles isotropes (ICA) et les colles anisotropes (ACA). Ces propriétés s’appliquent également pour la colle selon la présente invention. La colle ICA est électriquement conductrice dans toutes les directions. La colle ICA est utilisée pour des applications telles que le collage de puce contact et le collage de composant CMS. La colle ACA contient des particules conductrices spécifiques, qui conduit l’électricité dans une seule direction. Cette colle est utilisée dans de nombreuses structures sensibles sur les circuits, comme pour le collage des structures d’antennes RFID, les connexions LCD ou encore PCB flexibles. By “matrix of electrically conductive adhesive”, it is understood in the context of the present invention a substance constituting the matrix, electrically conductive, making it possible to make electrical contacts, while ensuring adhesion to the substrate to which it is applied. . In the present invention, it is the adhesive matrix which essentially allows the adhesive properties of the adhesive composition "matrix + pigment". The substrate on which the glue is applied may be more or less sensitive to temperature, which justifies the use of a matrix, the implementation of which avoids temperatures which can alter said substrate. In addition, the matrices of electrically conductive adhesives, which are typically of a polymeric nature such as a resin, are generally much more flexible than conventional welds, which allows them to better resist vibrations or external shocks. There are two types of electrically conductive adhesives: isotropic adhesives (ICA) and anisotropic adhesives (ACA). These properties also apply to the adhesive according to the present invention. ICA glue is electrically conductive in all directions. ICA glue is used for applications such as contact chip bonding and SMD component bonding. ACA glue contains specific conductive particles, which conduct electricity in one direction. This adhesive is used in many sensitive structures on circuits, such as for bonding RFID antenna structures, LCD connections or flexible PCBs.
[0019] Toute viscosité des colles peut être applicable. Les colles conductrices (de l’art ainsi que selon la présente invention) sont typiquement d’une viscosité comprise entre une à plusieurs centaines de mPas (par exemple 200 mPas) jusqu’à plusieurs dizaines de milliers de mPas (par exemple 50 000 mPas). Dans le cadre de la présente invention, les colles utilisées ont préférentiellement une viscosité comprise entre 2000 et 15000 mPas. Any viscosity of the adhesives may be applicable. Conductive adhesives (both in the art and according to the present invention) typically have a viscosity of between one to several hundred mPas (for example 200 mPas) up to several tens of thousands of mPas (for example 50,000 mPas ). As part of the present invention, the adhesives used preferably have a viscosity of between 2000 and 15000 mPas.
[0020] Toute nature chimique connue des colles électriquement conductrices est applicable à l’objet de la présente invention. Les colles peuvent ainsi être par exemple des colles époxy, polyimides, acrylates, polyester, etc. sensibles ou non aux rayonnements UV. S’il est possible que des composés métalliques puissent se trouver dans la matrice de ces colles, une concentration forte de ces composés métalliques n’est pas souhaitable dans le cadre de la présente invention : il serait alors en effet plus difficile (voire impossible) d’éliminer ces métaux par une application laser sans altérer le substrat. Les matrices de colles conductrices sur le marché contiennent typiquement des métaux à des concentrations permettant la mise en oeuvre de la présente invention sans en altérer le substrat. Ainsi, la présence de ces composés métalliques n’étant pas obligatoire quant à la mise en œuvre de la présente invention, il est laissé à l’homme du métier l’appréciation de leurs ajouts dans les colles de la présente invention afin d’obtenir des effets complémentaires désirés. Any known chemical nature of electrically conductive adhesives is applicable to the subject of the present invention. The adhesives can thus be, for example, epoxy, polyimide, acrylate, polyester adhesives, etc. sensitive or not to UV radiation. If it is possible that metal compounds may be present in the matrix of these adhesives, a high concentration of these metal compounds is not desirable in the context of the present invention: it would then be more difficult (if not impossible) to remove these metals by a laser application without altering the substrate. The matrices of conductive adhesives on the market typically contain metals at concentrations allowing the implementation of the present invention without altering the substrate. Thus, the presence of these metallic compounds not being obligatory as for the implementation of the present invention, it is left to the skilled person the appreciation of their additions in the adhesives of the present invention in order to obtain desired additional effects.
[0021] En outre, dans le cadre de la présente invention, par « colle conductrice électrique » ou « matrice de colle conductrice », il est compris de manière générale que la colle/matrice peut être figée ou pas. Ainsi, la matrice de la colle peut être plus ou moins organisée, plus ou moins souple, plus ou moins figée. In addition, in the context of the present invention, by "electrically conductive adhesive" or "conductive adhesive matrix", it is generally understood that the adhesive / matrix can be fixed or not. Thus, the adhesive matrix can be more or less organized, more or less flexible, more or less fixed.
[0022] Par « pigment et/ou colorant sensible à un rayonnement laser », il est compris dans le cadre de la présente invention toute entité chimique dont l’entropie va augmenter lorsque ledit pigment et/ou colorant est soumis à un ou plusieurs rayonnement(s) laser(s). Il est implicite dans le cadre de la présente invention que le pigment/colorant est ajouté à une concentration ne bloquant pas la conductivité de la colle, ou à la quantité souhaitée pour ne pas bloquer les propriétés d’adhésion de la colle. By "pigment and / or dye sensitive to laser radiation", it is understood in the context of the present invention any chemical entity whose entropy will increase when said pigment and / or dye is subjected to one or more radiation (s) laser (s). It is implicit in the context of the present invention that the pigment / dye is added at a concentration that does not block the conductivity of the adhesive, or in the desired amount so as not to block the adhesion properties of the adhesive.
[0023] Par « construction ou reconstruction de circuits électriques », il est compris dans le contexte de la présente invention le fait de créer des liaisons conductrices électriques entre au moins deux points permettant un échange d’électricité (i.e. sur un circuit électrique). Si cette/ces liaisons ont précédemment existées, il s’agira d’une reconstruction (i.e. une réparation), s’il s’agit de la création d’une nouvelle liaison, alors on parlera de construction. By “construction or reconstruction of electrical circuits”, it is understood in the context of the present invention to create electrical conductive connections between at least two points allowing an exchange of electricity (ie on an electrical circuit). If this / these links previously existed, it will be a reconstruction (ie a repair), if it is the creation of a new link, then we will speak of construction.
[0024] Par « circuit électrique », il est compris dans le contexte de la présente invention au moins une liaison physique, préférentiellement un réseau de liaisons physiques, permettant l’échange d’électricité. On parlera de circuit électronique dans le contexte de la présente invention lorsque la liaison ou le réseau de liaisons est compris ou inscrit sur et/ou dans un substrat isolant, tel qu’une plaque de silicium, époxy isolant, silicone, etc. qui peut être lui-même incorporé dans un appareil, tel qu’un ordinateur (un ordinateur de bureau ou un serveur informatique), ou d’un appareil électronique portable, tel qu’un téléphone portable, un smart phone, une tablette informatique, un ordinateur portable, un GPS, un caméscope, un appareil photo, un dictaphone, une caméra embarquée, un ordinateur embarqué dans un véhicule, un enregistreur embarqué dans un véhicule. Dans le contexte de la présente invention, un circuit microélectronique est un circuit électronique qui comprend des liaisons électriques physiques permettant l’échange d’électricité, lesquelles liaisons sont de taille micrométrique (i.e. compris entre 1 et 1000 pm, préférentiellement inférieur à 1000 miti, 500 pm, 250 pm, 100 pm, 50 pm, 10 pm, 5 pm ou encore inférieur à 3 pm). By "electrical circuit", it is understood in the context of the present invention at least one physical link, preferably a network of physical links, allowing the exchange of electricity. We will speak of an electronic circuit in the context of the present invention when the bond or the network of bonds is understood or inscribed on and / or in an insulating substrate, such as a silicon wafer, insulating epoxy, silicone, etc. which can itself be incorporated into a device, such as a computer (a desktop computer or a computer server), or of a portable electronic device, such as a mobile phone, a smart phone, a computer tablet, a laptop, a GPS, a camcorder, a camera, a dictaphone, an on-board camera, a computer in a vehicle, a recorder in a vehicle. In the context of the present invention, a microelectronic circuit is an electronic circuit which includes physical electrical connections allowing the exchange of electricity, which connections are of micrometric size (ie between 1 and 1000 μm, preferably less than 1000 μm, 500 pm, 250 pm, 100 pm, 50 pm, 10 pm, 5 pm or even less than 3 pm).
[0025] Par « recueil ou réalisation d’un spectre d’absorption » selon la présente invention, il est compris qu’un spectre d’absorption d’un composé (liquide ou solide), ou d’un mélange de composés, est réalisé dans les conditions usuelles d’analyse (équivalent au terme « réalisation »), ou est obtenu dans des bases de données tierces, telles que des publications scientifiques (équivalent au terme « recueil »). By "collection or realization of an absorption spectrum" according to the present invention, it is understood that an absorption spectrum of a compound (liquid or solid), or of a mixture of compounds, is carried out under the usual conditions of analysis (equivalent to the term "achievement"), or is obtained from third-party databases, such as scientific publications (equivalent to the term "collection").
[0026] Par « liens conducteurs électriques » selon la présente invention, on entend des fils de diamètre nanométrique (entre 1 et 10 nm) et micrométrique (entre 1 et 1000 pm, préférentiellement inférieurs à 1000 pm, 500 pm, 250 pm, 100 pm, 50 pm, 10 pm, 5 pm ou encore inférieur à 3 pm). By “electrical conductive links” according to the present invention, is meant wires of nanometric diameter (between 1 and 10 nm) and micrometric diameter (between 1 and 1000 pm, preferably less than 1000 pm, 500 pm, 250 pm, 100 pm, 50 pm, 10 pm, 5 pm or even less than 3 pm).
[0027] DESCRIPTION DETAILLEE DETAILED DESCRIPTION
[0028] Composition de colle conductrice [0029] La composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que sa matrice est adaptée à son utilisation dans l’électronique et/ou à la microélectronique. Ainsi, l’avantage de la présente invention, est que la composition de colle conductrice électrique peut être une colle conductrice électrique industrielle classique (sans pigment) constituant la matrice, à laquelle on ajoute le pigment et/ou colorant selon la présente invention. Composition of conductive adhesive The electrically conductive adhesive composition according to the present invention can be characterized in that its matrix is suitable for its use in electronics and / or in microelectronics. Thus, the advantage of the present invention is that the composition of electrically conductive adhesive can be a conventional industrial electrically conductive adhesive (without pigment) constituting the matrix, to which the pigment and / or dye according to the present invention is added.
[0030] Ainsi, la composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que la matrice est une colle telle que définie ci-dessus (cf. Définitions) et peut être par exemple polymérique (époxy, polyimides, acrylates, polyester, etc.). Thus, the composition of electrically conductive adhesive according to the present invention can be characterized in that the matrix is an adhesive as defined above (cf. Definitions) and can for example be polymeric (epoxy, polyimides, acrylates, polyester, etc.).
[0031] De manière préférée, la composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que la matrice est une colle conductrice électrique choisie dans la liste consistant en les colles époxy, silicones, polyuréthanes, polyimides, acrylates. La polymérisation de ces colles peut être réalisée par l’application d’une variation de température (e.g. chauffage) ou l’emploi d’un catalyseur. Par exemple, la composition de colle conductrice électrique selon la présente invention peut être polymérisée par application d’une température supérieure à 95°C pendant un temps compris entre quelques secondes et 1 heure, par exemple entre 1 à 10 minutes. De manière classique, les colles époxy par exemple, peuvent être à 1 ou 2 composants selon les ratios usuels de l’art (typiquement 1 pour 1 en masse). La composition de colle conductrice électrique selon la présente invention peut être en outre caractérisée en ce qu’elle est exempte de solvants. Une colle conductrice électrique utilisée dans le cadre de la présente invention comme matrice peut être Polytec EC15IL® (base epoxy), Polytec EC151 L-frozen® (epoxy), Polytec EC101® (base epoxy), Polytec EC101- L-frozen® (epoxy), Polytec EC1 12L-frozen® (epoxy), Polytec EC201® (epoxy), Polytec EC242-frozen® (epoxy), Polytec EC262-2® (epoxy), Polytec PU-1000® (polyuréthane), Polytec SB1227® (epoxy), Electrolube Silver Conductive Adhesive Paint®, RS Pro Silver Conductive Adhesive Paint ®, RS Pro Silver Conductive Adhesive Paint, RS Pro Silver Conductive Adhesive Epoxy®, Chemtronics Silver Conductive Adhesive Epoxy®, MG Chemicals Silver Conductive Adhesive Epoxy®, Chemtronics Nickel Conductive Adhesive Paint®, MG Chemicals Carbon Adhesive Epoxy®, MG Chemicals Silver Conductive Adhesive Epoxy®, Chemtronics Silver Conductive Adhesive Paint®, etc. Preferably, the composition of electrically conductive adhesive according to the present invention can be characterized in that the matrix is an electrically conductive adhesive chosen from the list consisting of epoxy adhesives, silicones, polyurethanes, polyimides, acrylates. The polymerization of these adhesives can be carried out by the application of a temperature variation (eg heating) or the use of a catalyst. For example, the composition of electrically conductive adhesive according to the present invention can be polymerized by applying a temperature above 95 ° C. for a time between a few seconds and 1 hour, for example between 1 to 10 minutes. Conventionally, epoxy adhesives for example, can be 1 or 2 components according to the usual ratios of the art (typically 1 to 1 by mass). The electrically conductive adhesive composition according to the present invention can be further characterized in that it is free from solvents. An electrically conductive adhesive used in the context of the present invention as a matrix can be Polytec EC15IL® (epoxy base), Polytec EC151 L-frozen® (epoxy), Polytec EC101® (epoxy base), Polytec EC101- L-frozen® ( epoxy), Polytec EC1 12L-frozen® (epoxy), Polytec EC201® (epoxy), Polytec EC242-frozen® (epoxy), Polytec EC262-2® (epoxy), Polytec PU-1000® (polyurethane), Polytec SB1227® (epoxy), Electrolube Silver Conductive Adhesive Paint®, RS Pro Silver Conductive Adhesive Paint ®, RS Pro Silver Conductive Adhesive Paint, RS Pro Silver Conductive Adhesive Epoxy®, Chemtronics Silver Conductive Adhesive Epoxy®, MG Chemicals Silver Conductive Adhesive Epoxy®, Chemtronics Nickel Conductive Adhesive Paint®, MG Chemicals Carbon Adhesive Epoxy®, MG Chemicals Silver Conductive Adhesive Epoxy®, Chemtronics Silver Conductive Adhesive Paint®, etc.
[0032] Les colles conductrices électriques selon la présente invention peuvent être adaptées à l’adhérence aux métaux (métaux ferreux ou non ferreux), aux verres, aux céramiques, et/ou aux plastiques. Classiquement, les supports sont nettoyés avant application de la/des compositions de colle(s) conductrice(s) électrique(s) selon la présente invention. The electrical conductive adhesives according to the present invention can be adapted to adhesion to metals (ferrous or non-ferrous metals), glasses, ceramics, and / or plastics. Conventionally, the supports are cleaned before application of the composition (s) of electrically conductive adhesive (s) according to the present invention.
[0033] Les colles conductrices électriques selon la présente invention peuvent être adaptées aux circuits électriques flexibles ou aux substrats insensibles aux facteurs de contraintes physiques extérieur (i.e. support ayant une rigidité suffisante). The electrical conductive adhesives according to the present invention can be adapted to flexible electrical circuits or to substrates insensitive to external physical stress factors (i.e. support having sufficient rigidity).
[0034] De manière préférée, les colles conductrices électriques utilisables selon la présente invention sont adaptées à la liaison de fusibles céramiques, à l’impression d’antennes à la liaison de tout type de composants, plus particulièrement à la liaison de composant sensibles à la chaleur, à la liaison de composants flexibles, à la liaison de circuits flexibles, au conducteurs imprimés flexibles sur support souple et/ou à l’impression sur écran. Preferably, the electrically conductive adhesives which can be used according to the present invention are suitable for the connection of ceramic fuses, for the printing of antennas for the binding of all types of components, more particularly to the binding of components sensitive to heat, to the connection of flexible components, to the connection of flexible circuits, to the flexible printed conductors on flexible support and / or to screen printing.
[0035] Les colles conductrices électriques peuvent contenir un ou plusieurs agents permettant le passage du courant électrique, tels que des atomes et/ou ions métalliques, et/ou de particules conductrices. Ainsi, les colles conductrices électriques selon la présente invention peuvent contenir du graphite, de l’argent, du fer, du nickel, du zinc, du cuivre, des sels organiques et/ou minéraux. Electrically conductive adhesives may contain one or more agents allowing the passage of electric current, such as metal atoms and / or ions, and / or conductive particles. Thus, the electrically conductive adhesives according to the present invention can contain graphite, silver, iron, nickel, zinc, copper, organic and / or mineral salts.
[0036] Un exemple de colle conductrice électrique utilisable selon l’invention peut comprendre les composés suivants : acétate de N-butyle, argent, acétate de 2- butoxyéthyle, 2-méthoxy-1-méthyléthyle acétate, 3,6-diazaoctanéthylènediamine. An example of an electrically conductive adhesive which can be used according to the invention may comprise the following compounds: N-butyl acetate, silver, 2-butoxyethyl acetate, 2-methoxy-1-methylethyl acetate, 3,6-diazaoctanethylenediamine.
[0037] Un autre exemple de colle conductrice électrique utilisable selon l’invention peut comprendre les composés suivants : éther d’alkyl (en C1 à C8) glycidyle, oxyde d’aluminium, bisphénol-A, résine époxy, noir de carbone, phénol époxy, résine novalaque, de l’éther diglycidyle glycol néopentyle, de l’oxyde de zinc. Another example of an electrically conductive adhesive which can be used according to the invention can comprise the following compounds: alkyl ether (C1 to C8) glycidyl, aluminum oxide, bisphenol-A, epoxy resin, carbon black, phenol epoxy, novalaque resin, diglycidyl ether neopentyl glycol, zinc oxide.
[0038] La composition de colle conductrice électrique utilisable comme matrice selon la présente invention peut être caractérisée en ce qu’elle a une viscosité à 23°C comprise entre 500 et 50000 mPa.s avant polymérisation, par exemple inférieure à 45000 mPa.s, inférieure à 25000 mPa.s, inférieure à 10000 mPa.s, inférieure à 6000mPa.s, préférentiellement inférieure à 5000mPa.s. De manière préférée, la composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que la matrice a une viscosité à 23°C avant polymérisation comprise entre 1000 et 45000 mPa.s, entre 2000 et 25000 mPa.s, entre 3000 et 10000 mPa.s, préférentiellement entre 4000 et 8000 mPa.s. The composition of electrically conductive adhesive usable as a matrix according to the present invention can be characterized in that it has a viscosity at 23 ° C. between 500 and 50,000 mPa.s before polymerization, for example less than 45,000 mPa.s, less than 25,000 mPa.s, less than 10,000 mPa.s, less than 6,000 mPa.s, preferably less than 5,000 mPa.s. Preferably, the composition of electrically conductive adhesive according to the present invention can be characterized in that the matrix has a viscosity at 23 ° C. before polymerization of between 1000 and 45000 mPa.s, between 2000 and 25000 mPa.s, between 3000 and 10,000 mPa.s, preferably between 4,000 and 8,000 mPa.s.
[0039] La composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que ledit pigment et/ou colorant absorbe à une longueur d’onde comprise entre 500 nm et 1 100 nm, préférentiellement entre 532 nm et 1064 nm. Par exemple, la longueur d’onde est comprise entre 500 et 600 nm, préférentiellement entre 510 et 550 nm, plus préférentiellement entre 520 et 540 nm, encore plus préférentiellement entre 530 et 535 nm, telle que 532 nm. Par exemple, la longueur d’onde est comprise entre 1000 et 1 100 nm, préférentiellement entre 1040 et 1090 nm, plus préférentiellement entre 1050 et 1080 nm, encore plus préférentiellement entre 1060 et 1070 nm, telle que 1064 nm. The electrically conductive adhesive composition according to the present invention can be characterized in that said pigment and / or dye absorbs at a wavelength between 500 nm and 1100 nm, preferably between 532 nm and 1064 nm. For example, the wavelength is between 500 and 600 nm, preferably between 510 and 550 nm, more preferably between 520 and 540 nm, even more preferably between 530 and 535 nm, such as 532 nm. For example, the wavelength is between 1000 and 1100 nm, preferably between 1040 and 1090 nm, more preferably between 1050 and 1080 nm, even more preferably between 1060 and 1070 nm, such as 1064 nm.
[0040] La composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que ledit pigment et/ou colorant est choisi parmi l’Indigo, l’Erichrome Black T et le Noir de Sudan. De manière avantageuse, ledit pigment et/ou colorant est choisi parmi l’Indigo, et l’Erichrome Black T pour leur propriété de conductivité électrique. De manière plus avantageuse, ledit pigment et/ou colorant est l’Erichrome Black T pour son incorporation homogène dans les colles conductrices. The composition of electrically conductive adhesive according to the present invention can be characterized in that said pigment and / or dye is chosen from Indigo, Erichrome Black T and Sudan Black. Advantageously, said pigment and / or dye is chosen from Indigo and Erichrome Black T for their property of electrical conductivity. More advantageously, said pigment and / or dye is Erichrome Black T for its homogeneous incorporation in conductive adhesives.
[0041] La composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que la quantité dudit colorant et/ou pigment permet d’obtenir une résistance de la composition de colle conductrice électrique une fois figée apte à permettre un lien électrique pendant au moins une heure. De manière préférée, une fois figée la composition de colle conductrice électrique selon la présente invention permet un lien électrique pendant au moins 6 heures. De manière plus préférée, une fois figée la composition de colle conductrice électrique selon la présente invention permet un lien électrique pendant au moins 24 heures, au moins une semaine au moins un mois. De manière encore plus préférée, une fois figée la composition de colle conductrice électrique selon la présente invention permet un lien électrique pendant au moins un an. The composition of electrically conductive glue according to the present invention can be characterized in that the amount of said dye and / or pigment makes it possible to obtain a resistance of the composition of electrically conductive glue once frozen capable of allowing an electrical connection during at least an hour. Preferably, once the composition of electrically conductive adhesive according to the present invention has been fixed, it allows an electrical connection for at least 6 hours. More preferably, once the composition of electrically conductive adhesive according to the present invention has been fixed, it allows an electrical connection for at least 24 hours, at least a week at least a month. Even more preferably, once the composition of electrically conductive adhesive according to the present invention has been fixed, it allows an electrical connection for at least one year.
[0042] L’objet de la présente invention concerne donc une composition de colle conductrice électrique pour la création ou la reconstruction de circuits électrique, préférentiellement de circuits électroniques et/ou microélectroniques. Ainsi l’objet de la présente invention concerne une méthode de création ou la reconstruction de circuits électrique, préférentiellement de circuits électroniques et/ou microélectroniques impliquant l’utilisation d’une composition de colle conductrice électrique selon la présente invention. The object of the present invention therefore relates to an electrically conductive adhesive composition for the creation or reconstruction of electrical circuits, preferably electronic and / or microelectronic circuits. Thus, the subject of the present invention relates to a method of creating or reconstructing electrical circuits, preferably electronic and / or microelectronic circuits involving the use of an electrically conductive adhesive composition according to the present invention.
[0043] La composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que le circuit électrique provient ou est à destination d’un appareil électronique fixe, tel qu’un ordinateur de bureau ou un serveur informatique, ou d’un appareil électronique portable, tel qu’un téléphone portable, un smart phone, une tablette informatique, un ordinateur portable, un GPS, un caméscope, un appareil photo, un dictaphone, une caméra embarquée, un ordinateur embarqué dans un véhicule, un enregistreur embarqué dans un véhicule. The composition of electrically conductive adhesive according to the present invention can be characterized in that the electrical circuit comes from or is intended for a fixed electronic device, such as a desktop computer or a computer server, or a portable electronic device, such as a mobile phone, a smart phone, a computer tablet, a laptop, a GPS, a camcorder, a camera, a dictaphone, an on-board camera, a computer on board a vehicle, an on-board recorder in a vehicle.
[0044] La composition de colle conductrice électrique selon la présente invention peut être caractérisée en ce que le circuit électrique est ou provient d’une carte mère informatique, d’une carte vidéo informatique, d’une mémoire informatique telle qu’un disque dur SSD, une carte SD ou micro SD ou encore une carte flash, d’un processeur, d’une barrette de ram, d’une carte SIM. The composition of electrically conductive adhesive according to the present invention can be characterized in that the electrical circuit is or comes from a computer motherboard, a computer video card, a computer memory such as a hard disk. SSD, an SD or micro SD card or a flash card, a processor, a ram module, a SIM card.
[0045] Procédé de fabrication de colle conductrice Method of manufacturing conductive adhesive
[0046] L’objet de la présente invention concerne ainsi également le procédé de fabrication d’une composition de colle conductrice électrique tel que défini ci- dessus. The object of the present invention thus also relates to the process for the manufacture of an electrically conductive adhesive composition as defined above.
[0047] De manière préférée, le procédé de fabrication de la composition de colle conductrice électrique selon l’invention est effectué de manière industrielle, i.e. automatisée. Alternativement, le procédé de fabrication de la composition de colle conductrice électrique selon l’invention est effectué au cas par cas, à l’échelle du millilitre (compris entre 0,5 ml_ et 500 mL), ou à l’échelle du litre (compris entre 0,5 L et 50 L) et peut donc être effectué par un seul préparateur. Preferably, the process for manufacturing the composition of electrically conductive adhesive according to the invention is carried out industrially, ie automated. Alternatively, the process for manufacturing the composition of electrically conductive adhesive according to the invention is carried out on a case-by-case basis, on the scale of milliliter (between 0.5 ml_ and 500 ml), or on a liter scale (between 0.5 L and 50 L) and can therefore be carried out by a single preparer.
[0048] De manière préférée, lorsqu’il y a plusieurs ajouts de pigment(s) et/ou de colorant(s) à l’étape (b1 ), ces ajouts sont effectués de manière simultanée (diminution du nombre d’étapes du procédé). Alternativement, l’ajout de ces pigment(s) et/ou de colorant(s) peut être effectué de manière successive s’il y a un avantage à le faire par exemple au niveau de la solubilité des pigment(s) et/ou colorant(s) dans la matrice de colle conductrice. Preferably, when there are several additions of pigment (s) and / or dye (s) in step (b1), these additions are made simultaneously (reduction in the number of steps of the process). Alternatively, the addition of these pigment (s) and / or dye (s) can be carried out successively if there is an advantage in doing so, for example in terms of the solubility of the pigment (s) and / or dye (s) in the conductive glue matrix.
[0049] L’étape (c1 ) de mélange de la composition obtenue à l’étape (b1 ) est effectuée de manière à ce que tous le(s) pigment(s) et/ou colorant(s) soient réparties de manière uniforme dans la matrice de de colle conductrice. Step (c1) of mixing the composition obtained in step (b1) is carried out so that all of the pigment (s) and / or dye (s) are distributed uniformly in the matrix of conductive glue.
[0050] L’étape (d1 ) de récupération de la composition obtenue à l’étape (c1 ) est effectuée par toute manière adéquate connue dans l’art au vu des quantités impliquées. Une étape de conditionnement dans un récipient destiné à la vente et/ou au transport peut être ajouté à l’étape (d1 ). Step (d1) of recovery of the composition obtained in step (c1) is carried out by any suitable manner known in the art in view of the quantities involved. A packaging step in a container intended for sale and / or transport can be added to step (d1).
[0051] Procédé de sélection d’un colorant ou d’un pigment sensible à un rayonnement laser Method for selecting a dye or pigment sensitive to laser radiation
[0052] L’objet de la présente invention concerne ainsi également le procédé de sélection d’un colorant ou d’un pigment sensible à un rayonnement laser (pour la mise en œuvre du procédé de fabrication de la colle, et/ou de la méthode ou du procédé de construction ou reconstruction selon l’invention), tel que défini ci- dessus. The object of the present invention thus also relates to the method of selecting a dye or a pigment sensitive to laser radiation (for the implementation of the glue manufacturing process, and / or the construction or reconstruction method or method according to the invention), as defined above.
[0053] De manière préférée, l’étape (a2) de présélection d’un colorant, d’un pigment ou d’un mélange de ceux-ci, se fait en utilisant les données bibliographiques (tel qu’un catalogue de fournisseur) connues sur les pigments, colorants ou mélange de ceux-ci. Cette présélection peut être conditionnée par un appareillage laser (et donc les longueurs d’ondes déjà présélectionnées) déjà en utilisation pour éventuellement d’autres applications, ou tout simplement pour des questions de prix d’achat des pigments, colorants ou d’un mélange de ceux-ci. Preferably, step (a2) of preselecting a dye, a pigment or a mixture thereof, is done using bibliographic data (such as a supplier catalog) known on pigments, dyes or a mixture thereof. This preselection can be conditioned by a laser apparatus (and therefore the wavelengths already preselected) already in use for possibly other applications, or quite simply for questions of purchase price of the pigments, dyes or of a mixture. of these.
[0054] L’étape (b2) de recueil ou de réalisation d’un spectre d’absorption du colorant ou pigment présélectionné à l’étape (a2) est réalisée par une consultation des données bibliographiques connues (« recueil ») du colorant ou pigment présélectionné à l’étape (a2), ou d’une technique classique dans l’art d’analyse spectrométrique d’absorption. Step (b2) of collecting or producing an absorption spectrum of the dye or pigment preselected in step (a2) is carried out by consulting the known bibliographic data (“collection”) of the dye or pigment preselected in step (a2), or of a conventional technique in the art of absorption spectrometric analysis.
[0055] De manière préférée, l’étape de sélection (c2) de la longueur d’onde du rayonnement laser à utiliser en fonction du spectre obtenu à l’étape (b2). Cette étape de sélection peut être un affinage de la longueur d’onde de l’appareil déjà en possession de l’utilisateur, si cela est possible. Une autre façon de réaliser l’invention est de présélectionner plusieurs colorants, pigments et/ou mélanges de ceux-ci, de recueillir pour chaque échantillons les longueurs d’ondes d’absorption, puis de sélectionner les/les échantillons présentant la/les meilleures absorptions à une longueur d’onde prédéfinie (dans le cas où l’on est déjà en possession du matériel laser). Preferably, the selection step (c2) of the wavelength of the laser radiation to be used as a function of the spectrum obtained in step (b2). This selection step can be a refinement of the wavelength of the device already in the possession of the user, if possible. Another way of carrying out the invention is to preselect several dyes, pigments and / or mixtures thereof, to collect for each samples the absorption wavelengths, then to select the sample (s) having the best absorptions at a predefined wavelength (in the case where one is already in possession of the laser material).
[0056] De manière préférée, le procédé de sélection d’un colorant ou d’un pigment sensible à un rayonnement laser (pour la mise en oeuvre du procédé de fabrication de la colle, et/ou de la méthode ou du procédé de construction ou reconstruction selon l’invention), peut être caractérisé en ce que l’étape (c2) de sélection de la longueur d’onde du rayonnement laser est faite pour une longueur d’onde représentant l’un des 10 pics les plus intenses du spectre d’absorption obtenus à l’étape (b2). Preferably, the method of selecting a dye or a pigment sensitive to laser radiation (for the implementation of the method of manufacturing the glue, and / or the method or the construction method or reconstruction according to the invention), can be characterized in that the step (c2) of selecting the wavelength of the laser radiation is carried out for a wavelength representing one of the 10 most intense peaks of the absorption spectrum obtained in step (b2).
[0057] De manière préférée, le procédé de sélection d’un colorant ou d’un pigment sensible à un rayonnement laser (pour la mise en oeuvre du procédé de fabrication de la colle, et/ou de la méthode ou du procédé de construction ou reconstruction selon l’invention), peut être caractérisé en ce qu’il comprend une étape additionnelle (d2) de détermination de la puissance du rayonnement laser sélectionné à l’étape (c2), permettant de garder l’intégrité du composant électronique à construire ou à reconstruire, caractérisé en ce que l’étape (d2) est une exposition à différentes puissances du rayonnement laser sélectionné à l’étape (c2) d’un support de même nature que le support du composant électronique à construire ou à reconstruire, et de choisir une puissance inférieure à celle altérant la surface du support pour un temps donné de traitement.  Preferably, the method of selecting a dye or a pigment sensitive to laser radiation (for the implementation of the method of manufacturing the adhesive, and / or the method or the construction method or reconstruction according to the invention), can be characterized in that it comprises an additional step (d2) of determining the power of the laser radiation selected in step (c2), making it possible to keep the integrity of the electronic component at build or reconstruct, characterized in that step (d2) is an exposure to different powers of the laser radiation selected in step (c2) of a support of the same nature as the support of the electronic component to be built or to reconstruct , and to choose a power lower than that altering the surface of the support for a given treatment time.
[0058] De manière avantageuse, il est en outre possible d’effectuer une étape (e2) de test de conductivité d’une colle figée selon la présente invention comprenant le colorant et/ou pigment sélectionné afin de s’assurer que ce mélange puisse être utilisé en électronique. Advantageously, it is also possible to carry out a step (e2) of testing the conductivity of a fixed adhesive according to the present invention comprising the dye and / or pigment selected to ensure that this mixture can be used in electronics.
[0059] Procédé de construction ou reconstruction d’un circuit électrique Method of construction or reconstruction of an electrical circuit
[0060] L’objet de la présente invention concerne également le procédé de construction ou reconstruction d’un circuit électrique, préférentiellement électronique ou microélectronique, tel que défini ci-dessus. The object of the present invention also relates to the method of construction or reconstruction of an electrical circuit, preferably electronic or microelectronic, as defined above.
[0061] De manière préférée, l’étape (a3) de dépôt de composition de colle conductrice électrique selon la présente invention sur une zone souhaitée d’un circuit électrique ou d’un support pour circuit électrique, est effectuée grâce à un appareillage adapté à la taille dudit circuit électrique. Cette étape peut en outre s’effectuer via un contrôle visuel ou vidéo par le biais d’un microscope. Preferably, step (a3) of depositing composition of electrically conductive adhesive according to the present invention on a desired area of an electrical circuit or of a support for an electrical circuit, is carried out by means of suitable equipment. the size of said electrical circuit. This step can also be carried out via visual or video control using a microscope.
[0062] De manière préférée, l’étape (b3) optionnelle de traitement de la composition de colle conductrice électrique de l’étape (a3) pour que cette composition fige peut s’effectuer par un chauffage adapté, par un rayonnement électromagnétique tel qu’une application d’un rayonnement UV, et/ou une mise sous vide. Preferably, the optional step (b3) of treatment of the composition of electrically conductive adhesive of step (a3) so that this frozen composition can be carried out by suitable heating, by electromagnetic radiation such as 'an application of UV radiation, and / or a vacuum.
[0063] De manière préférée, l’étape (c3) d’application d’un rayonnement laser sur les zones à retirer de la composition conductrice électrique déposée à l’étape (a3) afin de construire ou reconstruire une portion conductrice voulue est effectuée grâce un laser d’ablation, pulsé ou non, par exemple de type « Ytterbium doped Fiber® » à 1064 nm. Preferably, step (c3) of applying laser radiation to the areas to be removed from the electrically conductive composition deposited in step (a3) in order to build or reconstruct a desired conductive portion is carried out using an ablation laser, pulsed or not, for example of the “Ytterbium doped Fiber®” type at 1064 nm.
[0064] Avantageusement, la puissance du laser peut être inférieure à 30W, 25W, 20W, 15W, 10W ou encore inférieure à 5W. Par exemple, la puissance du laser est comprise entre 5W et 30W, préférentiellement comprise entre 10W et 20W, par exemple 15W ± 3 W. Avantageusement, la surface de contact du laser appliqué est inférieure à 1 mm2, inférieure à 1000 pm2, inférieure à 100 pm2, inférieure à 10 pm2, inférieure à 1 pm2, ou encore inférieure à 0,1 pm2. Préférentiellement, le ratio entre puissance du laser appliqué et surface de contact dudit laser est inférieure à 1 W/pm2, inférieure à 0,5 W/pm2, inférieure à 0,3 W/pm2, inférieure à 0,25 W/pm2, inférieure à 0,2 W/pm2, inférieure à 0,15 W/pm2, inférieure à 0,1 W/pm2, ou encore inférieure à 0,05W/pm2. [0065] De manière préférée, l’étape (c3) d’application d’un rayonnement laser sur les zones à retirer de la composition conductrice électrique déposée à l’étape (a3) peut être caractérisé en ce que le temps de traitement permet de vaporiser toute la colle soumise au rayonnement laser. Advantageously, the power of the laser can be less than 30W, 25W, 20W, 15W, 10W or even less than 5W. For example, the laser power is between 5W and 30W, preferably between 10W and 20W, for example 15W ± 3 W. Advantageously, the contact surface of the laser applied is less than 1 mm 2 , less than 1000 pm 2 , less than 100 pm 2 , less than 10 pm 2 , less than 1 pm 2 , or even less than 0.1 pm 2 . Preferably, the ratio between the power of the applied laser and the contact surface of said laser is less than 1 W / pm 2 , less than 0.5 W / pm 2 , less than 0.3 W / pm 2 , less than 0.25 W / pm 2 , less than 0.2 W / pm 2 , less than 0.15 W / pm 2 , less than 0.1 W / pm 2 , or even less than 0.05W / pm 2 . Preferably, step (c3) of applying laser radiation to the areas to be removed from the electrically conductive composition deposited in step (a3) can be characterized in that the treatment time allows spray all the glue subjected to laser radiation.
[0066] De manière préférée, l’étape (d3) de récupération du circuit électrique ainsi traité est effectué sans traitement supplémentaire. Optionnellement, le circuit électrique peut être lavé avec un solvant adapté, tel qu’avec de l’eau dé-ionisé, ou un soufflage par de l’air ou un gaz neutre, afin de retirer les éventuels déchets provenant du traitement de l’étape (c3). Preferably, step (d3) of recovery of the electrical circuit thus treated is carried out without additional treatment. Optionally, the electrical circuit can be washed with a suitable solvent, such as with deionized water, or blowing with air or a neutral gas, in order to remove any waste from the treatment of the step (c3).
[0067] Dispositif de création de liens conducteurs électriques Device for creating electrical conductive links
[0068] L’objet de la présente invention concerne également le dispositif de création de liens conducteurs électriques comprenant un laser adapté à la mise en oeuvre du procédé de construction ou reconstruction d’un circuit électrique tel que décrit présentement. The object of the present invention also relates to the device for creating electrical conductive links comprising a laser suitable for implementing the method of construction or reconstruction of an electric circuit as described herein.
[0069] De manière préférée, le dispositif selon la présente invention comprend un laser adapté à la mise en oeuvre du procédé de construction ou reconstruction d’un circuit électrique selon la présente invention. Preferably, the device according to the present invention comprises a laser suitable for implementing the method of construction or reconstruction of an electrical circuit according to the present invention.
[0070] De manière préférée, le dispositif selon la présente invention peut être caractérisé en ce que ledit dispositif est un dispositif pour une mise en œuvre micrométrique. Preferably, the device according to the present invention can be characterized in that said device is a device for micrometric implementation.
[0071] Circuit électrique comprenant une composition de colle conductrice Electric circuit comprising a conductive adhesive composition
[0072] L’objet de la présente invention concerne également un circuit électrique, électronique ou microélectronique comprenant une composition de colle conductrice électrique (qui peut être figée ou non), tel que décrit présentement. The object of the present invention also relates to an electrical, electronic or microelectronic circuit comprising an electrically conductive adhesive composition (which may or may not be fixed), as described herein.
[0073] De manière préférée, l’objet de la présente invention concerne ainsi le circuit électrique, électronique ou microélectronique comprenant une composition de colle conductrice électrique susceptible d’être obtenu par le procédé tel que décrit présentement. Preferably, the subject of the present invention thus relates to the electrical, electronic or microelectronic circuit comprising an electrically conductive adhesive composition capable of being obtained by the method as described herein.
[0074] FIGURES [0075] [Fig. 1] : Photographie d’une prise de vue au microscope électronique de l’accès à la mémoire silicium après deux attaques physiques (laser). Il peut être constaté la dégradation de plusieurs fils de liaison. FIGURES [Fig. 1]: Photograph of a shot using an electron microscope of access to the silicon memory after two physical attacks (laser). Degradation of several connecting wires can be observed.
[0076] [Fig. 2] : Figure 2A, 2B : Photographies de prises de vues au microscope électronique à balayage de fils de liaison partiellement détruits lors d'attaques physiques. [Fig. 2]: Figure 2A, 2B: Photographs of shots taken using a scanning electron microscope of connecting wires partially destroyed during physical attacks.
Figure 2C : Agrandissement d’une photographie de prise de vue au microscope électronique de fils de liaison partiellement détruits lors d'une attaque physique. Il peut être constaté la dégradation de plusieurs fils de liaison. Figure 2C: Enlargement of an electron microscope photograph of connection wires partially destroyed during a physical attack. Degradation of several connecting wires can be observed.
[0077] [Fig. 3] : Graphique montrant la mesure de la profondeur moyenne retirée (moyenne sur 5 mesures) par l’application d’un laser sur une colle industrielle conductrice exempte de colorant ou pigment (mesure prise en utilisant un microscope plan focal). [Fig. 3]: Graph showing the measurement of the average depth removed (average over 5 measurements) by the application of a laser on a conductive industrial adhesive free of dye or pigment (measurement taken using a focal plane microscope).
[0078] Il peut être vu que le laser vaporise la colle conductrice industrielle mais à partir d'une puissance de 60% de la puissance laser maximale (30W). La problématique est qu'avec une telle puissance, le laser endommage le composant électronique de façon irréversible (destruction des données, risque de toucher le silicium). It can be seen that the laser vaporizes the industrial conductive glue but from a power of 60% of the maximum laser power (30W). The problem is that with such power, the laser irreversibly damages the electronic component (destruction of the data, risk of touching the silicon).
[0079][Fig.4] : Spectre de réflexion infrarouge de l'indigo, faible réflexion et forte absorption à 1064nm. [Fig.4]: Infrared reflection spectrum of indigo, low reflection and high absorption at 1064nm.
[0080] [Fig.5] : Figure 5A : Graphique montrant la mesure utilisant un microscope plan focal de la profondeur moyenne retirée (moyenne sur 2 mesures) par l’application d’un laser sur une colle industrielle conductrice contenant de l’indigo à hauteur de 0% en masse (courbe la plus basse - témoin) ; 8,8% en masse (courbe intermédiaire en hauteur) et 25% en masse (courbe la plus haute). Il peut être constaté que les courbes pour 8,5% et 25 % sont relativement proches. [Fig.5]: Figure 5A: Graph showing the measurement using a focal plane microscope of the average depth removed (average over 2 measurements) by the application of a laser on an industrial conductive adhesive containing indigo 0% by mass (lowest curve - control); 8.8% by mass (intermediate height curve) and 25% by mass (highest curve). It can be seen that the curves for 8.5% and 25% are relatively close.
Figure 5B : Graphique montrant la mesure utilisant un microscope plan focal de la profondeur moyenne retirée (moyenne sur 2 mesures) par l’application d’un laser sur une colle industrielle conductrice contenant de « l’Erichrome Black T » à hauteurde 0% en masse (courbe la plus basse - témoin) ; 12% en masse (seconde courbe en partant du bas), 36% en masse (troisième courbe en partant du bas) et 60% en masse (quatrième courbe en partant du bas). Il peut être constaté que les troisième et quatrièmes courbes pour 36% et 60 % sont quasiment juxtaposées. Figure 5B: Graph showing the measurement using a focal plane microscope of the average depth removed (average over 2 measurements) by the application of a laser on a conductive industrial adhesive containing “Erichrome Black T” at a height of 0% mass (lowest curve - control); 12% by mass (second curve from the bottom), 36% by mass (third curve from the bottom) and 60% by mass (fourth curve from the bottom). It can be seen that the third and fourth curves for 36% and 60% are almost juxtaposed.
[0081 ] [Fig. 6] : Figure 6 A : Représentation de l’intensité spatiale d’un faisceau laser selon le plan (X, Y) perpendiculaire à l’axe de propagation. Le centre du faisceau est là où la plus grande énergie (Emax) est mesurée (assurant ainsi la précision du traitement lors de l’application du laser). Le sigle « w » représente l’écart de distance entre Emax et 0, 1 35 Emax. Il correspond au rayon du faisceau laser pris à 0, 1 35 (inverse de la constante irrationnelle de Néper au carré) de l’irradiance maximale. Le sigle « e » représente la constante irrationnelle de Néper valant 2,71 828. [Fig. 6]: Figure 6 A: Representation of the spatial intensity of a laser beam along the plane (X, Y) perpendicular to the axis of propagation. The center of the beam is where the greatest energy (Emax) is measured (thus ensuring the precision of the treatment when applying the laser). The acronym "w" represents the distance difference between Emax and 0.135 Emax. It corresponds to the radius of the laser beam taken at 0.135 (inverse of Néper's irrational constant squared) of the maximum irradiance. The acronym "e" represents the irrational constant of Neper equal to 2.71,828.
Figure 6B : Représentation de l’intensité spatiale du faisceau laser selon l’axe z perpendiculaire à l’axe de propagation. Le sigle « Wo » représente le rayon du faisceau laser au point « waist ». Le sigle « R(z) » représente le module en coordonnées cylindriques, le sigle « Q » représente l’azimut en coordonnées cylindriques et le sigle « z » représente la cote en coordonnées cylindriques. Le sigle « ZR» représente la constante de Rayleigh. Le point « V2Wo » représente le rayon du faisceau laser pris à la distance de Rayleigh du « waist ». Figure 6B: Representation of the spatial intensity of the laser beam along the z axis perpendicular to the propagation axis. The acronym "Wo" represents the radius of the laser beam at the point "waist". The acronym "R (z)" represents the module in cylindrical coordinates, the acronym "Q" represents the azimuth in cylindrical coordinates and the acronym "z" represents the dimension in cylindrical coordinates. The acronym "ZR" represents the Rayleigh constant. The point “V2Wo” represents the radius of the laser beam taken at the Rayleigh distance from the “waist”.
[0082] [Fig. 7] : Photographies de prises de vues au microscope électronique à différentes étapes du procédé selon l’invention. La figure 7A représente un fil de liaison cassé avant traitement. La figure 7B représente la première étape d’application de la colle issue de la présente invention sur la portion de la photographie en figure 7A. La figure 7C représente le trajet du spot laser «Ytterbium doped Fiber » à lambda =1064nm. La figure 7D représente la portion de la photographie en figure 7A réparée avec un micro-collage conducteur de 15micro-metre réalisé par attaque laser. Le passage électrique est assuré dans le cas 7D, ce qui a permis de lire les informations contenues sur la partie endommagée. [Fig. 7]: Photographs of shots taken with an electron microscope at different stages of the process according to the invention. FIG. 7A represents a broken connecting wire before treatment. FIG. 7B represents the first step of applying the glue from the present invention to the portion of the photograph in FIG. 7A. FIG. 7C represents the path of the “Ytterbium doped Fiber” laser spot at lambda = 1064nm. FIG. 7D represents the portion of the photograph in FIG. 7A repaired with a conductive micro-bonding of 15m micro-meter produced by laser attack. The electrical passage is ensured in case 7D, which made it possible to read the information contained on the damaged part.
[0083] EXEMPLES EXAMPLES
[0084] Généralités General
[0085] La colle utilisée dans le cadre de la présente invention est de la « polytec EC151 L® » qui est une colle solide à deux composants, électriquement conductrice, de type époxy. Sa viscosité constatée est de 4800 mPa.s. Sa durée de vie à température ambiante constatée est de 2 jours. A une température de 60°C pendant 90 minutes, une prise (polymérisation) suffisante a été constatée. Un traitement à 150°C pendant 15 minutes ou à 180°C pendant 40 secondes sont également applicables pour sa polymérisation selon le cas d’espèce. La température de dégradation thermique indiquée est de 400°C avec des températures intermédiaires (sans dégradations) comprises entre -55°C et 300°C. La chimie particulière des colles époxy permet une polymérisation rapide à une température élevée (i.e. supérieure à 100°C) et permet d’être sollicitée (garder ses propriétés physico-chimiques) également à des températures élevées (jusqu’à 300°C, voire 400°C). The adhesive used in the context of the present invention is "polytec EC151 L®" which is a solid adhesive with two components, electrically conductive, epoxy type. Its observed viscosity is 4800 mPa.s. Its lifespan at room temperature observed is 2 days. At a temperature of 60 ° C for 90 minutes, sufficient setting (polymerization) was observed. A treatment at 150 ° C for 15 minutes or at 180 ° C for 40 seconds are also applicable for its polymerization depending on the case. The indicated thermal degradation temperature is 400 ° C with intermediate temperatures (without degradations) between -55 ° C and 300 ° C. The particular chemistry of epoxy adhesives allows rapid polymerization at a high temperature (ie above 100 ° C) and allows to be stressed (keep its physicochemical properties) also at high temperatures (up to 300 ° C, or even 400 ° C).
[0086] Le laser utilisé dans le cadre de la présente invention est un laser « Nd :Yag ® », de puissance de 30 W, ajustable, opérant dans le cadre de la présente invention à 1064nm (voire 532 nm selon le cas d’espèce).  The laser used in the context of the present invention is an "Nd: Yag ®" laser, with a power of 30 W, adjustable, operating in the context of the present invention at 1064nm (or even 532 nm depending on the case of species).
[0087] Concernant le choix des colorants et/ou pigments, il a été choisi « l’Indigo » (Sigma Aldrich® CAS 482-89-3), « l’Erichrome Black T » (Prolabo® CAS 1787-61- 7) et « le Noir de Sudan » Réactifs® RAL 4197-25-5). Les spectres IR ont été pris (cf. figure 4 pour l’indigo à titre d’illustration), ce qui a permis de sélectionner ces colorants et/ou pigments. Regarding the choice of dyes and / or pigments, "Indigo" (Sigma Aldrich® CAS 482-89-3) and "Erichrome Black T" (Prolabo® CAS 1787-61- 7) were chosen. ) and “Sudan Black” Reagents® RAL 4197-25-5). The IR spectra were taken (cf. FIG. 4 for the indigo by way of illustration), which made it possible to select these dyes and / or pigments.
[0088] Par exemple, le dioxyde de titane qui n’absorbe pas à 1064nm (longueur d’onde utilisée) n’a pas été retenu pour la suite de l’étude. For example, titanium dioxide which does not absorb at 1064nm (wavelength used) was not used for the rest of the study.
[0089] Exemple 1 : détermination des colles comprenant les colorants/pigments Example 1: Determination of adhesives comprising dyes / pigments
[0090] Différents mélanges avec différents colorants et/ou pigments ont été réalisés. Different mixtures with different dyes and / or pigments have been produced.
Ces mélanges figés de colles ont été soumis à des rayonnements laser de différentes puissances (40%, 50%, 60% et 70% de 30W) et les quantités de matériaux ainsi retirés, ont été mesurées par l’utilisation d’un microscope plan focal. Ainsi, il a pu être mesuré l’irradiation nécessaire pour dégrader la colle sans pigment ou colorant (cf. figure 3). Une puissance de 50% du laser du laboratoire est suffisante pour ce faire. [0091] Les résultats obtenus pour les colles (« polytec EC151 L® ») comprenant de « l’Indigo », « l’Erichrome Black T » ou « le Noir de Sudan » sont regroupés dans le tableau 1 (cf. également figures 5A et 5B). These fixed mixtures of glues were subjected to laser radiation of different powers (40%, 50%, 60% and 70% of 30W) and the quantities of materials thus removed were measured by the use of a plane microscope focal. Thus, it was possible to measure the irradiation necessary to degrade the glue without pigment or dye (see Figure 3). A power of 50% of the laboratory laser is sufficient to do this. The results obtained for the adhesives (“polytec EC151 L®”) comprising “Indigo”, “Erichrome Black T” or “Black of Sudan” are grouped in Table 1 (cf. also figures 5A and 5B).
[0092] Résultats pour différents mélanges testés : [0093] [Tableaux 1] Results for various mixtures tested: [Tables 1]
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000019_0001
Figure imgf000020_0001
[0094] * Le Noir de Sudan utilisé à plus de 5% en masse dans la colle selon la présente invention rend le mélange isolant électriquement. Il est possible de simplement vérifier la conductivité des mélanges selon la présente invention avant leur application. * Sudan black used at more than 5% by mass in the adhesive according to the present invention makes the mixture electrically insulating. It is possible to simply check the conductivity of the mixtures according to the present invention before their application.
[0095] Exemple 2 : Procédé de reconstruction d’un circuit de microélectronique Example 2: Method for reconstructing a microelectronic circuit
[0096] Il a été réalisé selon la présente invention, une réparation d’une mémoire de type eMMC, telle qu’illustrée en figure 7. It was carried out according to the present invention, a repair of an eMMC type memory, as illustrated in FIG. 7.
[0097] Un décapage au laser a été fait sur la pièce à réparer, endommageant des connexions micrométriques, comme constaté sur la figure 7A. Une grande densité de connexion fait qu’il est impossible d’utiliser des techniques de l’art antérieur. Une colle selon la présente invention contenant 35% de « Erichrome Black T » a été appliqué sous forme d’une couche mince de 50pm d’épaisseur aux endroits endommagées en utilisant un micro-instrument de type « Tedpella Micro- Spade 0.025mm ® » (figure 7B). Laser stripping was carried out on the part to be repaired, damaging micrometric connections, as noted in FIG. 7A. A high connection density makes it impossible to use techniques of the prior art. An adhesive according to the present invention containing 35% of “Erichrome Black T” was applied in the form of a thin layer of 50 μm thick to the damaged areas using a micro-instrument of the “Tedpella Micro-Spade 0.025mm®” type. (Figure 7B).
[0098] Un masque définissant le chemin où appliquer le laser a été définit (figure 7C). A mask defining the path where to apply the laser has been defined (FIG. 7C).
[0099] Quatre passages d’un laser 1064nm à 40% de puissance (30W max) ont permis d’obtenir une mémoire réparée (figure 7D), utilisable pour récupérer des informations inaccessibles avant traitement. Four passes of a 1064nm laser at 40% power (30W max) made it possible to obtain a repaired memory (FIG. 7D), usable for recovering inaccessible information before processing.
[0100] La technique utilisée avec les moyens du laboratoire ont permis de générer des connexions de 15pm dans ce cas. Il est tout à fait envisageable d’utiliser des moyens connus bien plus précis pour obtenir des résultats plus fins encore. The technique used with the laboratory means made it possible to generate 15pm connections in this case. It is quite possible to use much more precise known means to obtain even finer results.

Claims

Revendications Claims
[Revendication 1] (Composition de colle conductrice électrique caractérisée en ce qu’elle comprend :  [Claim 1] (Composition of electrically conductive adhesive, characterized in that it comprises:
- une matrice de colle conductrice électrique, - a matrix of electrically conductive adhesive,
- au moins un pigment et/ou au moins un colorant sensible à un rayonnement laser. - at least one pigment and / or at least one dye sensitive to laser radiation.
[Revendication 2] Composition de colle conductrice électrique selon la revendication 1 , caractérisée en ce que ledit pigment et/ou colorant absorbe à une longueur d’onde comprise entre 500 nm et 1 100 nm, préférentiellement entre 532nm et 1064 nm. [Claim 2] Composition of electrically conductive adhesive according to claim 1, characterized in that said pigment and / or dye absorbs at a wavelength between 500 nm and 1100 nm, preferably between 532nm and 1064 nm.
[Revendication 3] Composition de colle conductrice électrique selon la revendication 1 ou 2, pour la création ou la reconstruction de circuits électrique, préférentiellement de circuits électroniques et/ou microélectroniques. [Claim 3] Composition of electrically conductive adhesive according to claim 1 or 2, for the creation or reconstruction of electrical circuits, preferably electronic and / or microelectronic circuits.
[Revendication 4] Procédé de fabrication d’une composition de colle conductrice électrique selon l’une quelconque des revendications 1 à 3, comprenant les étapes successives suivantes : [Claim 4] Method for manufacturing an electrically conductive adhesive composition according to any one of claims 1 to 3, comprising the following successive steps:
(a1 ) ajout dans un récipient d’une matrice de colle conductrice électrique, (a1) addition of an electrically conductive glue matrix to a container,
(b1 ) ajout dans le récipient de l’étape (a1 ) d’au moins un pigment et/ou d’au moins un colorant sensible à un rayonnement laser, (b1) adding to the container of step (a1) at least one pigment and / or at least one dye sensitive to laser radiation,
(c1 ) mélange de la composition obtenue à l’étape (b1 ) , et (c1) mixing the composition obtained in step (b1), and
(d1 ) récupération de la composition obtenue à l’étape (c1 ). (d1) recovery of the composition obtained in step (c1).
[Revendication 5] Utilisation d’une composition de colle conductrice électrique selon l’une quelconque des revendications 1 à 3 pour la construction ou la reconstruction de circuits électriques. [Claim 5] Use of an electrically conductive adhesive composition according to any one of claims 1 to 3 for the construction or reconstruction of electrical circuits.
[Revendication 6] Procédé de sélection d’un colorant ou d’un pigment sensible à un rayonnement laser caractérisé par les étapes successives suivantes : (a2) présélection d’un colorant, d’un pigment ou d’un mélange de ceux- ci, [Claim 6] Method for selecting a dye or a pigment sensitive to laser radiation, characterized by the following successive steps: (a2) preselection of a dye, a pigment or a mixture thereof,
(b2) recueil ou réalisation d’un spectre d’absorption du colorant ou pigment présélectionné à l’étape (a2) ; et (b2) collection or production of an absorption spectrum of the dye or pigment preselected in step (a2); and
(c2) sélection de la longueur d’onde du rayonnement laser à utiliser en fonction du spectre obtenu à l’étape (b2). (c2) selection of the wavelength of the laser radiation to be used as a function of the spectrum obtained in step (b2).
[Revendication 7] Procédé de construction ou reconstruction d’un circuit électrique, préférentiellement électronique ou microélectronique, caractérisé par les étapes successives suivantes : [Claim 7] Method of constructing or reconstructing an electrical circuit, preferably electronic or microelectronic, characterized by the following successive steps:
(a3) dépôt de composition de colle conductrice électrique selon la présente invention sur une zone souhaitée d’un circuit électrique ou d’un support pour circuit électrique, (a3) depositing an electrically conductive adhesive composition according to the present invention on a desired area of an electrical circuit or of a support for an electrical circuit,
(b3) optionnellement, traitement de la composition de colle conductrice électrique de l’étape (a3) pour que cette composition fige, (b3) optionally, treatment of the composition of electrically conductive adhesive of step (a3) so that this composition freezes,
(c3) application d’un rayonnement laser sur les zones à retirer de la composition conductrice électrique déposée à l’étape (a3) afin de construire ou reconstruire une portion conductrice voulue ; et (c3) applying laser radiation to the areas to be removed from the electrical conductive composition deposited in step (a3) in order to build or reconstruct a desired conductive portion; and
(d3) récupération du circuit électrique ainsi traité. (d3) recovery of the electrical circuit thus treated.
[Revendication 8] Dispositif de création de liens conducteurs électriques comprenant un laser adapté à la mise en œuvre du procédé selon la revendication 7. [Claim 8] Device for creating electrical conductive links comprising a laser suitable for implementing the method according to claim 7.
[Revendication 9] Circuit électrique, électronique ou microélectronique comprenant une composition de colle conductrice électrique selon l’une quelconque des revendications 1 à 3. [Claim 9] Electrical, electronic or microelectronic circuit comprising an electrically conductive adhesive composition according to any one of claims 1 to 3.
[Revendication 10] Appareil électrique ou électronique comprenant au moins un circuit électrique, électronique ou microélectronique selon la revendication 9. [Claim 10] An electrical or electronic device comprising at least one electrical, electronic or microelectronic circuit according to claim 9.
PCT/FR2019/000178 2018-10-24 2019-10-24 Electrically conductive adhesive and (re)generation of (micro)electric circuits WO2020084202A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7227095B2 (en) 2003-08-06 2007-06-05 Micron Technology, Inc. Wire bonders and methods of wire-bonding
WO2011101788A1 (en) * 2010-02-17 2011-08-25 Basf Se Process for producing electrically conductive bonds between solar cells
JP2017008260A (en) * 2015-06-25 2017-01-12 株式会社タムラ製作所 Anisotropy conductive adhesive and printed wiring board prepared therewith

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7227095B2 (en) 2003-08-06 2007-06-05 Micron Technology, Inc. Wire bonders and methods of wire-bonding
WO2011101788A1 (en) * 2010-02-17 2011-08-25 Basf Se Process for producing electrically conductive bonds between solar cells
JP2017008260A (en) * 2015-06-25 2017-01-12 株式会社タムラ製作所 Anisotropy conductive adhesive and printed wiring board prepared therewith

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