• 专利附录
  • 专利说明
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  • 类似技术
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    • 专利摘要:
    The invention relates to a process for depositing a polymeric coating, through which it can be soldered, on a printed circuit board without coating, which process comprises the use of a medium low power and a low pressure plasma polymerization in a polymerization chamber, of an organosilane precursor monomer which is introduced into said polymerization chamber by means of a carrier gas, wherein said organosilane of Formula (I) is Y1-X-Y2 or (II) - [Si (CH3) 2-X-] N-, wherein: X is O or NH; Y1 is -Si (Y3) (Y4) Y5; Y2 is Si (Y3 ') (Y4') Y5 '; and Y3, Y4, Y5, Y3 ', Y4', and Y5 'are each individually H or an alkyl group of up to 10 carbon atoms; the monomer of formula (II) is cyclic in which n is 2 to 10; wherein of Y3, Y4 and Y5 at most one group is hydrogen, and wherein of Y3 ', Y4' and Y5 'at most one group is hydrogen; and wherein the total number of carbon atoms is not more than 20.
    公开号:BE1021398B1
    申请号:E2014/0009
    申请日:2014-01-07
    公开日:2015-11-16
    发明作者:Filip Legein；Peter Martens；Eva Rogge
    申请人:Europlasma Nv；
    IPC主号:
    专利说明:

    Surface coatings
    The present invention relates to surface coatings and processes for making them. In particular, the invention is related to surfaces on which a cover layer through which soldering can be applied is deposited and the deposition of these layers by means of a monomer; and in particular the use of such processes to deposit a coating through which soldering can be deposited on a printed circuit board (PCB).
    A printed circuit board (PCB) is made of a non-conductive material on which conductive circuits are arranged. The conductive circuits are typically made of copper and function as a connection between electrical components connected to the circuit board, e.g. by soldering.
    The principle of depositing a coating on a PCB is known in the prior art, the aim being to protect the conductive circuits from environmental factors, in particular to prevent or delay the occurrence of oxidation. Polymeric coatings through which soldering can be used are used in the prior art so that after depositing the coating, an electrical component can be connected to (or soldered to) the conductive circuits of the PCB without first having to remove the protective coating.
    Methods known in the art for depositing protective polymeric coatings on PCBs describe the use of gaseous fluorocarbon monomers that are polymerized on the surface via plasma deposition techniques. Examples of such monomers are tetrafluoromethane (CF 4), hexafluoroethane (C 2 F 6), hexafluoropropylene (C 3 F 6) or octafluoropropane (C 3 F 8). Such methods are described in WO 2008/102113.
    However, this specific class of precursor monomers require high power plasma techniques, such as, for example, 500 W in a 490 liter chamber, to initiate polymerization. Furthermore, large quantities of gas are required for this type of precursors, e.g. a flow rate of 100 sccm (cubic centimeters per minute - Eng. standard cubic centimeters per minute), and long deposition times, typically more than 5 minutes, to build up an acceptable coating thickness. For example, a deposition time of 7 minutes with the parameters given above will result in a coating of 28.4 nm thick.
    A problem that may arise with the use of the known high flow rate of monomer gas and / or high power is that the resulting polymeric coatings have a non-uniform thickness over the entire surface of the substrate. For example, a high power can lead to fragmentation of the monomer molecule, which can lead to unpredictable deposition of the polymer and, consequently, an unacceptable quality of the coating. Non-uniform deposition can lead to non-uniform thickness of the coating. This is disadvantageous because on the one hand zones can arise where the thickness of the cover layer is higher than the optimum thickness, which makes the soldering of electrical components extremely difficult. On the other hand, certain zones may have a thickness that is lower than the optimum thickness - or even the absence of a cover layer - so that protection against oxidation and corrosion is substandard. A more uniform coating is also important for production-grade soldering, because the solder joints are always of the same quality, with fewer defects.
    Another problem that may arise when using precursor molecules as described above is that the deposited polymer has a limited hydrophobic character. Typical water contact angles that can be achieved with such polymeric coatings are up to 90 °. However, PCBs are often used in environments where corrosion or abrasion of the conductive circuits is easier, which leads to a shortened life of the electrical circuit. It is therefore desirable to deposit a coating with improved hydrophobic character, resulting in higher water contact angles, such as e.g. 95 ° and more, e.g. 100 ° and more.
    Another problem with methods that use fluorocarbons is a lack of control of the flow from monomer to and into the plasma chamber. Methods as described in the prior art typically use a "flow through" process in which monomer enters the chamber through an inlet, flows through the plasma zone (being the chamber) and is removed from the chamber through an outlet, the flow rate of the monomer is constant during the entire process. In other words, the amount of monomer gas entering the chamber is a constant, and the amount of gaseous monomer leaving the chamber is also a constant. Consequently, the monomer concentration is not homogeneous in the plasma zone, which can lead to non-homogeneous thicknesses of the coatings.
    Typical coatings from the prior art are often soft coatings that have limited resistance to scratches and abrasion. Coatings deposited by polymerization of fluorocarbon chemistry tend to have a yellowish appearance, which may be visible after deposition of the coating. The present invention provides polymeric coatings that are hard and / or colorless and transparent. Such hard coatings are resistant to scratches and abrasion.
    The deposition of existing coatings is often accompanied by the formation of harmful or toxic by-products. The precursor monomers used in the present invention, and the resulting polymeric coating, are non-toxic and no harmful by-products are formed during deposition.
    Certain monomers described in the present invention can be used in forming gas barrier coatings for use in the food industry. These monomers can also be used in forming an insulating coating as in US 6,344,374, and are used in WO2010 / 134446 as a layer on top of a conductive film. Such known coatings are typically deposited in complex multi-step processes, often requiring an intermediate layer to ensure adequate adhesion of the gas barrier layer. This concept is described in, for example, WO2009 / 007654 and WO2012 / 171661.
    The present invention provides a coating that is deposited directly on the substrate without the need for an intermediate layer for improved adhesion. The coatings can also have a more uniform thickness over the substrate surface, are hydrophobic and scratch resistant.
    The use of the new processes described in this document lead to more elastic coatings, with improved in situ performance, without the formation of toxic by-products, and with improved uniformity, improved solderability and wettability during the soldering process, improved water-repellent character, improved scratch resistance , and the absence of discoloration of the substrate due to the transparent nature of the coating.
    A first aspect of the invention provides a process for depositing a polymeric coating through which soldering can be performed on an untreated circuit board - sometimes referred to as an "uncovered circuit board" or "naked" circuit board - during which a low average power and low pressure during the process plasma polymerization of an organosilane precursor monomer is carried out in a polymerization chamber, wherein the organosilane precursor monomer is introduced into the chamber by means of a carrier gas, and wherein the organosilane monomer has the formula (I) or (II) Y1-X-Y2 (I) or
    (II) wherein X is O or NH, Y 1 is -Si (Y 3) (Y 4) Y 5 and Y 2 is Si (Y 3) (Y 4 ') Y 5' wherein Y 3, Y 4, Y 5, Y 37, Y 47 and Y 5 - each independently H or an alkyl group of up to 10 carbon atoms; wherein from Y3, Y4 and Y5 at most one group is hydrogen, and wherein from Y3, Y4 and Y5 at most one group is hydrogen; the monomer of formula (II) is cyclic wherein n is 2 to 10; and the total number of carbon atoms is no more than 20.
    The alkyl groups can be linear or branched, but linear groups are preferred. Such alkyl groups are preferably methyl or ethyl groups, with methyl groups being preferred. Preferably, Y3, Y4, Y5, Y3, Y4 or Y5 are all alkyl groups.
    The monomer according to Formula I can contain six methyl groups, wherein the monomer according to Formula I can be hexamethyldisiloxane or hexamethyldisilazane.
    The monomer of Formula II can be a monomer in which n is 3, 4, 5 or 6. Preferably, the monomer of Formula II is octamethylcyclotetrasiloxane or hexamethylcyclotrisilazane.
    Preferably, the monomer used in the present invention is hexamethyldisiloxane.
    The plasma polymerization can be carried out in a continuous manner. The plasma polymerization can be carried out in a pulsed manner.
    Preferably, the organosilane precursor monomer is introduced into the chamber by means of a carrier gas.
    In some cases, the processes include an initial pre-treatment step to clean and / or etch and / or activate the printed circuit board (PCB) before depositing the coating. Pre-treatment in the form of an activation and / or cleaning and / or etching can be advantageous with regard to the adhesion, also called adhesion, and the crosslinking of the polymeric coating on the printed circuit board in the case of soiled substrates or substrates requiring some time has elapsed between the moment of production and the deposition of the polymeric coating.
    Adhesion of the polymeric coating on the nude printed circuit board is important in terms of the degree of corrosion protection of the substrate after depositing the coating. After producing a nude printed circuit board, the printed circuit board may be contaminated to a greater or lesser extent with residues from the production and manipulation of the printed circuit board. These residues are for the most part organic contamination or contamination in the form of oxides. When a soiled component is treated without a pre-treatment, a substantial part of the polymeric coating will bind to these residues, which may later lead to pinholes (with the exception of processes where the carrier gas itself is e.g. oxygen and therefore for cleaning and / or cleaning) whether the activation and / or etching can cause).
    Pre-treatment in the form of an activation and / or cleaning and / or etching removes the contamination and the residues and can therefore lead to an improved adhesion between the coating and the surface of the electronic component and / or the device that is subsequently placed on the printed circuit board will be soldered. An etching process can also be used to remove surface contamination of the copper from the conductive circuits before the coating is deposited.
    The person skilled in the art is able to decide whether or not a pre-treatment step is necessary, and this decision will depend on various factors such as the degree of contamination of the substrate on which a polymeric coating must be deposited. The degree of contamination can in turn depend on the degree of cleanliness of the production area where the substrate was produced.
    The pretreatment step is preferably carried out with reactive gases such as H 2, O 2 and etching reagents such as CF 4, but inert gases such as Ar, N 2 or He can also be used. Mixtures of the gases listed here can also be used.
    In a particular embodiment of the invention, the polymerization step in which the coating is deposited is carried out in the presence of a carrier gas, which may be the same gas (or mixture of gases) as used in the pre-treatment step.
    Preferably, the pretreatment is performed with O 2, Ar, or a mixture of O 2 and Ar, with O 2 currently being preferred.
    Preferably, the pretreatment step is carried out for 15 seconds to 15 minutes, for example 30 seconds to 10 minutes, preferably 45 seconds to 5 minutes, e.g. 5, 4, 3, 2, or 1 minutes. The duration of the pre-treatment depends on the precursor used, on the degree of soiling of the object to be treated, and on the device used to carry out the process.
    The power applied during the pre-treatment step can be applied in continuous mode or in pulsed mode.
    When a pre-treatment takes place, the polymeric coating is applied in a subsequent process step. Both processes can be performed in the same device.
    If no pre-treatment is applied, depositing the coating is the first and only step of the entire process.
    Pre-treatment is preferably applied before the polymeric coating is deposited.
    Preferably, the pretreatment and the deposition of the coating are carried out in the same device without the chamber being opened between the process steps, in order to prevent additional contamination from being deposited from the atmosphere on the substrate between the process steps.
    When the pretreatment is carried out with a continuous power, the power in a 490 I large plasma chamber will preferably be 5 to 5000 W, more preferably 25 to 4000 W, even more preferably 50 to 3000 W, take 100 to 2500 W, such as 200 to 2000 W, e.g. 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, or 200 W.
    When the pre-treatment is carried out with a pulsed power, the power in a 490 I large plasma chamber will preferably be 5 to 5000 W, more preferably 25 to 4000 W, even more preferably 50 to 3000 W, take 100 to 2500 W, such as 200 to 2000 W, e.g. 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, or 200 W.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching duration of about 0.05 to 50%, the optimum parameters depending on the gas or gas mixture being used.
    The polymeric coating through which soldering can take place can be formed by deposition in a plasma chamber, the plasma chamber comprising a first set of electrodes and a second set of electrodes, the first and the second set of electrodes being positioned on opposite sides of the chamber and wherein the first and the second set of electrodes consist of a plurality of radio frequency electrode layers ("RF") and / or a plurality of grounded electrode layers (ground electrode layer "M"). One or both of the first and the second sets of electrodes comprise an inner electrode layer and a pair of outer electrode layers. A set of electrodes consisting of an inner electrode layer and a pair of outer electrode layers could be referred to as a "tri-electrode".
    The inner electrode layer is preferably a radio frequency electrode layer ("RF") and the pair of outer electrode layers are preferably grounded layers (ground electrode layers "M").
    An alternative arrangement where the inner electrode layer is a grounded electrode layer and the pair of outer electrode layers of radio frequency electrode layers can also be used.
    If the inner electrode layer and / or the outer pair of electrode layers are of the radio frequency type, the or each electrode layer may include a heat controller, such as a substantially flat or channel-shaped portion to contain a controller fluid.
    If the inner electrode layer and / or the outer pair of electrode layers are of the grounded type, the or each electrode layer can be used without a heat controller. Electrode layers of this type can thus be a plate, grid or other configuration suitable for generating a plasma.
    The heat controller preferably consists of hollow tubes. The hollow tubes can form a path where the tubes fold around themselves at regular distances in a 180 ° bend, thus forming an electrode layer that is substantially flat in shape.
    The hollow tubes preferably have a diameter of about 2.5 to 100 mm, more preferably of about 5 to 50 mm, even more preferably a fan of about 5 to 30 mm, take up to 25, 20 or 15 mm, for example 10 mm.
    Preferably the hollow tubes have a wall thickness of about 0.1 to 10 mm, more preferably of about 0.25 to 5 mm, even more preferably of about 0.25 to 2.5 mm, take 1.5 mm.
    The distance between the hollow tubes before and after the bend of 180 ° is between 1 and 10 times the diameter of the tube, take about 3 to 8 times, for example 5 times the diameter of the tube.
    Preferably, the hollow tubes are made of a conductive material such as a metal, e.g. aluminum, stainless steel or copper. Other suitable conductive materials can also be considered.
    Preferably, the hollow tubes are filled with a fluid such as a liquid, e.g. water, oil or another liquid, or combinations thereof.
    The fluid can preferably be heated or cooled so that the plasma can be regulated over a wide temperature range, e.g. from 5 to 200 ° C.
    Preferably, the fluid controls the temperature of the plasma between about 20 and 90 ° C, more preferably between about 25 and 75 ° C, even more preferably between about 30 and 60 ° C, such as between 35 and 55 ° C.
    Furthermore, the temperature of the plasma chamber is preferably controlled and controlled, for example to avoid temperature differences within the chamber, and so to avoid cold points where the process gas can condense.
    For example, the door and some or all of the walls of the vacuum chamber can be provided with means that allow temperature control and control.
    The temperature control means preferably controls the temperature of the door and some or all of the walls of the room between 15 and 70 ° C, more preferably between 40 and 60 ° C.
    Furthermore, preferably also the pump and the monomer vapor supply system, the gas supply or feeds and all connectors between these components and the plasma chamber temperature are controlled to avoid cold points where the process gas or process gases could condense.
    Preferably, the power is applied over the radiofrequency electrode layer or layers via one or more connecting plates.
    The power of the deposition process can be applied in continuous mode or in pulsed mode.
    When the power for the deposition process is continuously applied in a 490 I large plasma chamber, the power is preferably about 5 to 5000 W, more preferably about 10 to 2000 W, even more preferably about 20 to 1500 W, take 250 to 1000 W, such as 50 to 750 W, e.g. 750, 725, 700, 675, 650, 625, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50 W.
    When the power for the deposition process is applied in a pulsed manner to a 490 I large plasma chamber, the power is preferably about 5 to 5000 W, more preferably about 10 to 4000 W, even more preferably about 20 to 3000 W, such as 30 to 2500 W, take 50 to 2000 W, such as 75 to 1500 W, take 100 to 1000 W, e.g. 1000, 975, 950, 925, 900, 875, 850, 825, 800, 775, 750, 725, 700, 675, 650, 625, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 190, 180, 175, 170, 160, 150, 140, 130, 125, 120, 110, or 100 W.
    For chambers with a larger volume, the applied power is typically slightly higher because the surface area of the electrode sets is larger due to the use of larger and / or more electrode layers.
    When applied in pulsed power, the pulsation frequency can range from 100 Hz to 10 kHz, with a switching duration of about 0.05 to 50%, the optimum parameters depending on the monomer being used.
    The optimum mode of the power and value of the applied power depend on the system used - the volume, number and dimensions of the electrode sets - and on the chemistry used.
    Preferably, the radio frequency electrode layer or layers generates a high frequency electric field at frequencies from 20 kHz to 2.45 GHz, more preferably from 40 kHz to 13.56 MHz, with a preference for 13.56 MHz.
    The plasma chamber preferably contains additional electrode sets, for example a third, fourth, fifth and sixth electrode set and so on.
    The or each electrode set can be constructed in the same way as the first and second electrode sets.
    Furthermore, the plasma chamber preferably includes means or means for locating and attaching the or each electrode set to the desired position or positions in the plasma chamber. An example of such a way is one or more connecting plates and / or the walls of the room itself.
    The plasma chamber preferably contains one or more inlets to introduce a monomer mixed with a carrier gas into the plasma chamber. The carrier gas is used to activate and ignite the plasma.
    Preferably, the plasma chamber contains at least two inlets.
    Preferably, each inlet feeds the monomer-and-carrier gas mixture into a monomer-and-carrier gas distribution system that uniformly distributes the mixture throughout the chamber. The inlet can, for example, feed a distribution system that in turn feeds the chamber.
    Each inlet can be spatially dispersed in the room. For example, a first inlet may be positioned in a first wall of the plasma chamber and a second inlet may be provided in a wall different from that where the first inlet is located, e.g., the opposite wall.
    The device also includes a system for supplying monomer vapor. Liquid monomer is evaporated in a controlled manner. Measured amounts of monomer vapor are supplied into the plasma chamber through a preferably temperature controlled supply line.
    Preferably, the monomer is evaporated at a temperature of 20 to 120 ° C, more preferably, 30 to 90 ° C, the optimum temperature depending on the physical properties of the monomer. The temperature of at least a part of the monomer vapor supply system can be controlled according to a sloping (rising or falling) temperature profile. The temperature profile will typically be slightly rising from the location where the monomer is evaporated, and this to the end of the supply line. In the vacuum chamber, the evaporated monomer will expand and the required temperatures at which no condensation will occur in the chamber and further to the pump will typically be lower than the temperatures of the supply line.
    The system further comprises a gas supply system, along which one or more different gases, such as a carrier gas or a combination of carrier gases, can be introduced into the vacuum chamber together with the evaporated monomer. A first container containing the first gas is connected to a first mass flow controller that controls the gas flow of the first gas.
    In some embodiments, there is further a second container containing a second gas, the second container being connected to a second mass flow controller that controls the gas flow of the second gas.
    In still other embodiments, there is further a third container containing a third gas, the third container being connected to a third mass flow controller that controls the gas flow of the third gas, and so on.
    After the or each gas has passed its respective mass flow controller, the or each gas is mixed with the monomer vapor before being introduced into the chamber. In certain embodiments, the supply line of the or each gas is heated after the mass flow controller to avoid temperature differences at the point where monomer vapor and the or each gas converge, as this can lead to condensation of the monomer-carrier gas mixture.
    Furthermore, the chamber preferably comprises a perforated container or drawer on which the substrates to be treated, e.g. a printed circuit board.
    Preferably, the substrate on which a coating is to be deposited is positioned on or in the container or drawer such that, during the process, a polymeric coating is deposited on each surface of the substrate.
    Preferably, there is a minimum distance of a few millimeters (mm) between the electrode set and the surface of the substrate on which a polymeric coating is to be deposited, more preferably 10 to 100 mm, such as 15 to 90 mm, take less than 80, 70, 60 or 50 mm, preferably 25 to 50 mm.
    Preferably, the deposited polymeric coating is a hydrophobic and scratch-resistant coating through which soldering can be deposited, deposited by polymerization of the monomers described in this invention.
    In the present invention, hydrophobic surfaces can be obtained with water contact angles of more than 95 °. In certain cases, water contact angles of more than 100 ° can be achieved.
    A system comprising a plasma chamber as described herein can be used to deposit the scratch-resistant solderable polymeric coatings.
    The system preferably comprises one or more gas outlets connected to the pump system.
    Preferably the system contains at least two gas outlets. The or each gas outlet is preferably positioned in a manner that evenly distributes the monomer throughout the chamber. The gas outlets can be connected to a distribution system.
    Although the inventors do not want or want to be linked to a certain theory, it is to be understood that the plasma generated between electrode sets of the system cannot be categorized as a pure primary or a pure secondary plasma. The inventors rather regard the plasma between the electrode sets as a new hybrid form of plasma, which is strong enough to be activated and remain ignited and, at the same time, gentle enough not to degrade the reactive monomers.
    As will be appreciated, a useful and unique aspect of the invention is that it is possible to generate a plasma on both sides of an object to be treated, such as a printed circuit board, when placed between two electrode sets. The symmetrical arrangement ensures that the plasma has a similar, preferably equal, intensity on each side of the object, and thus will cause the thickness of the cover layer to be similar or equal on both sides of the object.
    Preferably, low pressure plasma polymerization is used to deposit the coating.
    In this context, low pressure means that the operating pressure for plasma polymerization in a chamber up to 10000 I is in the order of 500 mTorr (66.7 Pa), and less, more preferably less than 250 mTorr (33.3 Pa), such as, for example, less than 150 m Torr (16.7 Pa).
    Preferably, the method allows depositing a polymeric coating with a thickness of 10 to 500 nm, more preferably of 10 to 200 nm, even more preferably of 20 to 150 nm, such as from 40 to 100 nm. The thickness of the coating can be less than 500 nm, for example less than 450, 400, 350, 300, 250, 200, 175, 150, 125, 100, 90, 80, 75, 70, 60, 50, or 40 nm , e.g. 30 nm.
    Preferably, the polymeric cover layer deposited according to the method described has a variation in uniformity of the thickness of less than 10%.
    The thickness and uniformity of the coating can depend on a number of factors, such as the duration of the deposition process, the nature of the monomer or monomers used, the flow rate of the monomer or monomers, the nature of the carrier gas (mixture) and its flow rate, the applied power and the method of application during the process step or process steps (if there is a pre-treatment step), the shape and dimensions of the plasma chamber, the sequence of the electrode layers within the electrode sets, the positioning of the electrode sets inside the chamber and / or the positioning of an untreated circuit board relative to the electrode sets.
    In any case, a person skilled in the art will be able to determine by routine techniques the parameters for the deposition process that are required for each given plasma chamber to obtain a thickness of the coating within a certain interval, and this for each (combination of organosilane monomer (or monomers) and carrier gas (s).
    Regarding the duration of the plasma process, typical deposition times are from 15 seconds to 10 minutes, such as from 30 seconds to 5 minutes, or, in particular, from 45 to 180 seconds. For example, when the organosilane monomer is hexamethyldisiloxane, the deposition time can be 30 to 120 seconds, such as 60 to 90 seconds.
    The above deposition times can be used in combination with one or more specific organosilane monomers, carrier gases, polymerization chambers, arrangement and construction of the electrode layers and the sets of electrodes, the applied powers for the deposition process and the way in which they are applied, monomer feed systems and flow rates. of monomer feed as described in the present invention. Furthermore, processes that make use of (a combination of) these parameters can be carried out with or without a pre-treatment step as described above.
    Furthermore, in certain embodiments of the invention, the untreated printed circuit board (PCB) is placed in the polymerization chamber such that: - the printed circuit board is placed between two electrode sets, each electrode set being positioned on opposite sides of the chamber, and each electrode set having multiple radiofrequency electrode layers (RF) and / or multiple grounded electrode layers (M); and - the distance from one side of the printed circuit board to the electrode set positioned on that side of the printed circuit board is approximately the same as (ie within 10% of, such as within 9, 8, 7, 6, 5, 4, 3, 2 or 1% of the distance from the opposite side of the PCB to the electrode set positioned on that opposite side.
    Positioning an untreated printed circuit board in this way, relative to the electrode sets, can help ensure uniformity of the coating on both sides of the printed circuit board.
    In the present invention, hydrophobic and scratch-resistant surfaces can be obtained with water contact angles of more than 95 °.
    The method may include supplying a constant stream of monomer into the plasma chamber through a monomer vapor feed system. The method may also include supplying a constant stream of gas, such as one or more carrier gases, by means of a mass flow controller.
    Preferably, the monomer vapor and the carrier gas (or carriers) are homogeneously mixed before being introduced into the chamber. A pressure control valve between the pump and the plasma chamber can control the pumping flow rate so that the desired process pressure can be obtained inside the plasma chamber.
    The pressure control valve is preferably more than 90% closed (to reduce the effective cross-section in the pipe to 10% of the maximum cross-section) in order to limit the flow through the chamber and the monomer-carrier gas (s) mixture more homogeneous over to spread the room.
    As soon as the monomer vapor pressure is stabilized in the chamber, the plasma is activated by switching on the radiofrequency electrode layers.
    Alternatively, the method may consist of introducing the monomer-carrier gas mixture into the plasma chamber in a first flow line; and changing the current sense to a second current sense after a predetermined time, for example 10 to 200 seconds, such as 30 to 180, or 40 to 150 seconds, e.g. less than 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30 or 20 seconds.
    Preferably, the flow sense of the monomer-carrier gas mixture is further changed, e.g. back to the first current sentence, or to one or more additional current sentences.
    It is preferable to introduce the monomer-carrier gas mixture into the plasma chamber in the first flow sense for 20 to 80% of the total process time, or 30 to 70% of the time, or 40 to 60% of the total time, or 50 % of the time.
    It is preferable to introduce the monomer-carrier gas mixture into the plasma chamber in the second flow sense for 20 to 80% of the total process time, or 30 to 70% of the time, or 40 to 60% of the total time, or 50 % of the time.
    Preferably, the process comprises introducing the organosilane precursor monomer into the plasma chamber by means of one or more carrier gases selected from H 2, I 2, O 2, N 2 O, CH 4, He or Ar, and / or a mixture of these gases. A single carrier gas is used in a preferred process. This is preferably O2 or Ar.
    The gas mixture (vaporized precursor monomer mixed with carrier gas (es)) introduced into the plasma chamber consists of approximately 1 to 50% carrier gas (es), more preferably approximately 5 to 30%, such as 10%.
    Preferably, the first and second flow sense are in an opposite sense. For example, during a process a monomer-carrier gas mixture can be introduced into the chamber via opposite walls.
    The cover layer is preferably deposited on one or more surfaces of the substrate.
    In a further aspect of the invention, a method is provided for depositing a polymeric coating on a substrate, e.g. a printed circuit board, which method comprises subjecting a monomer as described above to a low pressure continuous or pulsed plasma polymerization technique.
    In a still further aspect of the invention, the use of a monomer to deposit a scratch-resistant, transparent polymeric coating through which solder can be deposited, wherein the monomer is subjected to a low-pressure plasma polymerization technique in which the monomer is selected as described above.
    In a further aspect, the invention provides a scratch-resistant, transparent polymeric coating through which soldering can be effected, the coating being formed by depositing a monomer by means of a low pressure continuous or pulsed plasma polymerization technique, wherein the monomer is selected as described above .
    The solderable polymeric coating preferably also has hydrophobic and scratch-resistant properties. The coating is transparent and invisible to the human eye.
    Furthermore, preferably no toxic by-products are formed during the deposition of the solderable polymeric coating.
    In the present invention, hydrophobic surfaces can be obtained with water contact angles of more than 95 °. In some cases, water contact angles of more than 100 ° C can be achieved.
    The advantages of the chamber, the system and / or the method include - without being limiting - the polymerization of one or more highly reactive classes of monomers with low average powers; maximizing the diffusion of the monomer within the chamber to achieve a uniform thickness of the coating in a short time; minimizing harmful effects of the flow of process gas through the chamber; generating a gentle plasma that preferably has the same intensity on both sides of a substrate, e.g. a circuit board; the possibility of using both continuous mode and pulsed mode; the implementation of a way to change the flow of the monomer during deposition so that better uniformity is achieved; providing a way for precise control of the temperature to avoid unwanted temperature gradients.
    In order for the invention to be better understood, it will now be described by way of example with reference to the accompanying drawings, in which:
    Figure 1 shows a schematic representation of the configuration of the supply system, the vacuum chamber and the exhaust system.
    Referring to Figure 1, a plasma deposition system will now be described. The system comprises a vacuum chamber 11 in connection with a supply system 12 for introducing monomer into the chamber, a supply system 12 'for introducing one or more gases into the chamber via a common supply line 120, and an exhaust system 13 via a discharge line 130 .
    The supply system 12 for supplying monomer to the vacuum chamber comprises in succession a container, a first and a second container, a vacuum pressure gauge, e.g. a baratron, and a mass flow controller.
    The supply system 12 'for introducing one or more gases, such as one or more carrier gases, into the vacuum chamber for each gas separately in a sequential manner comprises a vessel or container containing the gas and a mass flow controller. After the respective mass flow regulators, the individual gas supply lines come together in a single gas supply line. This gas supply line comes together with the monomer vapor supply line in the supply line 120. The mixture of monomer vapor and the carrier gas (or carrier gases) is introduced into the vacuum chamber 11 via the supply line 120 and the first 121 and second 122 chamber inlet valve.
    The exhaust system 13 successively comprises a first 131 and second 132 outlet valve, a pressure control valve 133, a roots pump and a front vacuum pump 134 and an outlet valve.
    Multiple plasma electrode sets are located in the vacuum chamber 11, e.g. four sets, positioned in a stacked formation. Between each plasma electrode set is a drawer on which or in which the pieces to be treated are placed. The space between adjacent electrode sets is a test chamber. During use, one or more print boards are placed on or in the tray. The drawer is then placed between a pair of electrode sets in vacuum chamber 11.
    As soon as the drawer is placed in the vacuum chamber 11, the pressure in chamber 11 is lowered by evacuating the chamber 11. Afterwards, a mixture of gases consisting of a gaseous monomer (or a mixture of monomers) and one or more carrier gases is introduced into the chamber 11. Plasma is activated within chamber 11 by applying energy to the electrode sets. The carrier gas is used to activate the plasma so that polymerization of the monomer on the surface of the circuit board is initiated.
    Returning to Figure 1, examples of deposition processes will now be described. Initially, the pressure in the chamber 11 is reduced to a basic level vacuum, a basic pressure of typically 10 to 20 mTorr for a 490 I large plasma chamber, by means of the pump 134 with the first 131 and second 132 outlet valves open and the first 121 and second 122 chamber inlet valves closed.
    First, an amount of monomer is transferred from the container to the first container by means of a feed pump. A sufficient amount of monomer that allows to process a full day is typically transferred in one go. The monomers used are preferably in their liquid state. Thereafter, sufficient monomer for a single process is transferred from the first container to the second container by means of a dosing pump. The second container and thus also the monomer are brought to an elevated temperature, typically between 30 and 90 ° C, to evaporate the monomer. The selected temperature of the second container depends on the vapor pressure of the monomer, which is measured via a heated vacuum pressure meter.
    The or each carrier gas is transferred from its own container, e.g. the gas bottle itself, via its own mass flow controller to a single gas supply line. The homogeneous gas mixture is transferred from the gas supply line to supply line 120, together with the evaporated monomer when the monomer-carrier gas mixture is needed.
    In alternative embodiments, solid or gaseous monomers can be used. In embodiments where the monomer is a solid, it can also be evaporated, e.g. by heating in a container. In embodiments where the monomer is a gas, there is typically no need for evaporation.
    Once the desired pressure for the process, typically 40 to 50 mTorr, is achieved in vacuum chamber 11, the first inlet valve 131 is closed and the first monomer inlet valve 121 is opened. Consequently, when the monomer vapor feed system is open, monomer vapor produced in the second container will enter via the mass flow controller in the feed line 120, where it is mixed with one or more carrier gases that each have their own mass flow controller 12 'passed. This gas mixture (monomer-carrier gas) is introduced into vacuum chamber 11 via the open monomer inlet valve 122. The pressure within the chamber 11 is controlled at an operating level of typically 10 to 500 mTorr by either more monomer-carrier gas mixture within the pockets, or by to control the pressure control valve 133. Pressure control valve 133 is typically a butterfly valve.
    Once the pressure within the chamber 11 is stable, the electrode sets are activated by generating plasma in chamber 11. The carrier gas activates the plasma, which in turn activates the monomer and initiates polymerization on one or more surfaces of the printed circuit board . In this way the polymerization proceeds quickly, even at low pressure, typically 50 to 200 W, and at a low monomer flow rate, typically 50 to 100 standard cubic centimeters per minute (Eng. Standard cubic centimeters per minute, abbreviated as sccm), for a 490 I large plasma chamber.
    Carrier gas is used in low flow rates, typically 5 to 30% of the monomer flow. Sufficient monomer to achieve a desired coating thickness of 40 to 100 nm is usually polymerized after about 60 to 300 seconds, depending on the selected process parameters.
    During the process, the flow of the monomer through chamber 11 is exchanged via the first 121 and second 122 chamber inlet valves and the first 131 and second 132 outlet valves.
    For example, for 50% of the total process time, the first chamber inlet valve 121 is open and the first outlet valve 131 is closed (with the second chamber inlet valve 122 closed and the second outlet valve 132 open).
    For the remaining time, the second chamber inlet valve 122 is open and the second outlet valve 132 is closed (with the first chamber inlet valve 121 closed and the first outlet valve 131 closed).
    This means that during half of the process time monomer flows from one side of chamber 11 to the other side of chamber 11 and for the remaining time in the reverse direction. For example, half the time monomer flows from right to left and for the rest of the time the monomer flows from left to right. The flow sense of the monomer can be changed one or more times during a single process run.
    The supply 120 and outlet 130 lines are separated from each other. The supply line 120 can be coupled to a distribution system to distribute gas across chamber 11. The distribution system can be integrated into the wall of chamber 11 so that it can be kept at the same temperature as chamber 11. Further, in preferred embodiments, is the outlet line 130 positioned closer to the door of chamber 11 (rather than at the rear of chamber 11) to compensate for the fact that the intensity of the plasma tends to be higher at the electrode junction plates that typically in the rear wall of the room.
    In view of the safety of the operator, it is recommended at the end of the process that the chamber inlet valves 121 and 122 be closed and the chamber outlet valves 131 and 132 opened to reduce the pressure inside chamber 11 to the basic level to residual monomer to remove from the room. Once the basic pressure is reached, the chamber outlet valves 131 and 132 are closed and the chamber inlet valves 121 and 122 are opened. An inert gas such as nitrogen is introduced into the chamber from a separate container by opening valve 140. After the flushing cycle is completed, valve 140 is closed, and the pressure in the chamber 11 is reduced to atmospheric pressure by opening valve 150.
    After one or more process cycles, it is recommended to flush the monomer vapor feed system with an inert gas. For this purpose an inert gas line can be connected to the or each container. It is preferable to flush the supply line directly to the pump instead of through the chamber 11.
    The applicant has discovered that the use of an electrode set arrangement comprising an inner radiofrequency electrode layer (RF) and an outer pair of grounded electrode layers (M) improves the uniformity of the deposited polymeric coating.
    The applicant has also discovered that when organosilane polymeric coatings are deposited on a metal, the deposited coating functions as a flux. This makes the soldering operations easier.
    This flux has a number of advantages, including (i) Removing the cover layer so that components can be soldered to the conductive circuits; (ii) Removal of contamination and contamination on the copper tracks; (iii) Preventing oxidation when the temperature is raised to the solder reflow point; and (iv) Acting as an interface between the liquid solder and the cleaned copper webs.
    It is not uncommon for humidity and other gases to be present in the structure of a printed circuit board. When a polymeric coating is deposited on a printed circuit board, the moisture is trapped and can cause various problems during soldering and afterwards when the assembled printboards are subjected to varying temperatures. Humidity trapped can lead to increased loss currents and electromigration. Furthermore, humidity and other trapped gases can prevent a polymer from being deposited in the parts of the substrate surface where moisture and / or gases are trapped.
    It is therefore essential to remove trapped gases and moisture from the uncovered circuit board; this also ensures good adhesion (adhesion) between the polymeric coating and the printed circuit board. Captured gases and humidity can be removed by baking the structure before placing it in the plasma chamber, as is usual in conventional conformal coating techniques.
    The inventive process as described herein allows this degassing, or at least in part, to be carried out in the same chamber in which the pretreatment step - cleaning and / or activation and / or etching - and the plasma polymerization are carried out.
    The vacuum helps to remove moisture from the structure, improving adhesion and avoiding problems in further heat cycles during the life of the products. The printing interval! for degassing can range from 10 mTorr to 760 Torr at a temperature between 5 and 200 ° C, and can be performed in between 1 and 120 minutes, typically a few minutes.
    The degassing, activation and / or cleaning and / or etching, and the deposition process can all be performed in the same room, one after the other. An etching process can be used to remove surface contamination from the copper before an activation and deposition step takes place.
    A further aspect of the invention is that the frictional resistance with respect to other organic coatings is improved, which gives an improvement in the performance in a number of applications such as connectors and other sliding contacts.
    The conductive circuits on the substrate can consist of all possible conductive materials, such as metals, conductive polymers and conductive inks. Conductive polymers are hydrophilic in nature, leading to swelling, which can be avoided by applying the coating as described herein.
    Solder shielding varnishes are normally applied to printed circuit boards during the production process. These lacquers protect the metal conductors against oxidation and prevent the solder from flowing on the metallic connections, which limits the amount of solder in the soldered connection.
    Solder shield varnishes also limit the risk of short circuits between adjacent conductors due to soldering operations. Because the organosilane polymeric coating is removed only where a flux is applied, the rest of the printed circuit board, including the metallic conductors, remains covered with an efficient corrosion barrier. This also prevents the solder from flowing open on the conductive circuits and tracks during soldering, and this also minimizes the risk of solder bridges between conductors. Consequently, in some applications, the solder shield lacquer can be omitted.
    Further aspects of the invention are described with reference to the following Examples.
    Example 1
    An experiment was conducted to deposit a coating on a substrate according to the parameters of Table 1.
    Table 1: Process parameters according to a first example
    Results 1. Water repellency
    The water contact angle according to ASTM D5964-04 is used to determine the degree of hydrophobic character or wettability of a surface.
    Table 2: Test data for water repellency
    It is clear from Table 2 that the hydrophobic character in terms of water contact angles is equal or higher in the example according to the invention than for the prior art precursors.
    It should also be noted that the process time, power and flow rate for the coatings deposited according to the invention are all lower than for depositing coatings with chemistry known from the prior art. 2. Transparent coating
    The color change of objects on which a coating was deposited was measured according to ISO 105-J01 - L *, a *, b *, c *, CMC 2: 1. The results are expressed in a ΔΕ value. For coatings deposited according to the invention, the ΔΕ value was lower than 1, which means that no color change can be seen with the naked eye. 3. Non-toxic coatings
    The coatings deposited according to the present invention are non-toxic, as tested according to ISO 10993. 4. Deposition rate
    To demonstrate the deposition rate of different coatings, the thickness of the coatings was measured by ellipsometry. Coatings were deposited on glass plates with the treatment time being varied. The results can be found in Table 3.
    Table 3: Test data i.v.m. deposition rate
    To deposit a cover layer with C3F6 which has a thickness comparable to that of the cover layer of the invention according to Example 1, an approximately seven times longer process time is required. 5. Uniformity of the cover layer for single or multiple electrode layers per electrode set
    A conventional electrode arrangement consisting of a single electrode layer per electrode set was used. In such conventional arrangements, the top of the substrate is typically facing the radiofrequency electrode layer (RF) and a thicker topcoat is typically deposited on the top than on the bottom of the substrate, facing the grounded electrode layer (M).
    The multiple arrangement used in this example is made up of three electrode layers per electrode set: an inner RF electrode layer and a pair of outer electrode layers of the grounded type. The test pieces were placed between the two electrode sets, the first set being positioned on one side of the test pieces and the second set on the other side of the test pieces.
    1 A single electrode system is a conventional system as used in the prior art 2 A multiple electrode system is an inventive system as described above
    Table 4: Uniformity data
    As becomes clear from Table 4, the data shows that the coating of the invention covers both surfaces of the substrate in a more consistent and uniform manner. 6. The uniformity of the coating depends on the type of precursor
    The process parameters for a state-of-the-art precursor (C3F6) and for a precursor according to the invention (hexamethyldisiloxane HMDSO) were optimized with a view to ensuring that the coating layer was as uniform as possible.
    The standard deviation for the known coating was at least 25%. The standard deviation for the cover layer according to the invention was 9.25%.
    Moreover, the coating according to the invention was deposited at a lower power (about two and a half to five times less), and at a reduced process time. 7. Solderability of a printed circuit board with a plasma coating
    Different thicknesses of coatings were evaluated in terms of solderability through the coating. The printed circuit boards with a coating according to the invention, e.g. deposited with hexamethyldisiloxane (in continuous mode or in pulsed mode), all soldered well. The solderability is guaranteed in a wide range of thicknesses of the coatings, in this experiment from 10 to 170 nm. 8. Corrosion resistance
    The corrosion resistance was tested with a verification test, e.g. one gas, according to DIN EN ISO 3231. This test was developed in the past as a fast and efficient method for evaluating gold and nickel coatings on copper. • The test pieces were placed in a chamber filled with H2 SO3. The closed chamber was subsequently placed in an oven at 40 ° C. • After 24 hours, the test specimens were taken from the room and photographed. • The test pieces were placed in the chamber again. This was filled with a new amount of H 2 SO 3. The chamber was returned to the oven and the temperature was raised to 45 ° C. The chamber was kept at this temperature for four days, after which some traces of corrosion became visible on the test pieces with a polymeric coating. • Additional photos were taken at the end of the test.
    The result after 24 hours shows that the ENIG reference piece shows sufficient corrosion to make it unsuitable for use, while the pieces with a plasma polymeric coating according to the invention (Example 1) showed no signs of corrosion.
    After four additional days in the H2S03, the ENIG reference piece is heavily corroded with large places where copper oxide and nickel are visible. However, the coating according to the invention (Example 1) shows no corrosion at all, or only a few small spots.
    In this experiment, different precursors, different thicknesses of the coatings, and different modes of power (pulsed or continuous) showed the same excellent results.
    权利要求:
    Claims (17)
    [1]
    Conclusions
    A process for depositing a polymeric coating through which soldering can be carried out on a printed circuit board (PCB) without coating, which process comprises the use of medium low power and low pressure plasma polymerization in a polymerization chamber, of an organosilane precursor monomer introduced into said polymerization chamber by means of a carrier gas, said organosilane being of Formula (I) or (II) being Y1-X-Y2 (I) or

    (II) wherein: X is O or NH; Y 1 is -Si (Y 3) (Y 4) Y 5; Y2 is Si (Y30 (Y4 ') Y5'; Y3, Y4, Y5, Y3 ', Y4', and Y5- are each individually H or an alkyl group of up to 10 carbon atoms; the monomer of formula (II) is cyclic wherein n is 2 to 10, wherein at most one group of Y3, Y4 and Y5 is hydrogen, and wherein at most one of Y3, Y4 and Y5 is hydrogen, and wherein the total number of carbon atoms is no more than 20.
    [2]
    A process according to Claim 1, wherein each alkyl group present in the organosilane of Formula (I) is a linear alkyl group.
    [3]
    A process according to Claim 1 or Claim 2, wherein Y 3, Y 4, Y 5, Y 3, Y 4 or Y 5 are all alkyl groups.
    [4]
    A process according to any of Claims 1 to 3, wherein for Y 3, Y 4, Y 5, Y 3, Y 4 'or Y 5' each alkyl group is a methyl or an ethyl.
    [5]
    A process according to any of Claims 1 to 4, wherein the organosilane monomer of Formula I is hexamethyldisiloxane or hexamethyldisilazane.
    [6]
    A process according to any of Claims 1 to 4, wherein the processes further comprise a pre-treatment step to clean and / or etch and / or activate the printed circuit board (PCB) before a polymeric coating is deposited.
    [7]
    A process according to Claim 6, wherein the pre-treatment step is performed with H 2, O 2, N 2 O, CH 4, CF 4, He, Ar, N 2, He or mixtures thereof.
    [8]
    A process according to Claim 6 or Claim 7, wherein the pretreatment is performed with O 2, Ar, a mixture of O 2 and CF 4 or a mixture of O 2 and Ar.
    [9]
    A process according to any one of Claims 6 to 8, wherein the pre-treatment is performed for 15 seconds to 15 minutes, such as 45 seconds to 5 minutes, using a radio frequency power applied in continuous mode or pulsed mode.
    [10]
    A process according to any of Claims 6 to 9, wherein the pre-treatment step and the deposition step are performed in the same chamber without opening the chamber between the steps.
    [11]
    A process according to any of Claims 1 to 10, wherein the polymeric cover layer through which soldered can be formed by deposition in a plasma chamber, the plasma chamber comprising a first electrode set and a second electrode set, in which the first and the second electrode set are mounted to opposite chamber walls, and wherein the first and the second electrode sets comprise a plurality of radiofrequency electrode layers and / or a plurality of grounded electrode layers.
    [12]
    A process according to Claim 11, wherein one or both of the first and the second electrode sets comprises an inner electrode layer and a pair of outer electrode layers.
    [13]
    A process according to Claim 12, wherein the inner electrode layer is a radio frequency electrode layer or a grounded electrode layer and the outer electrode layers are grounded electrode layers or radio frequency electrode layers, respectively.
    [14]
    A process according to Claim 12 or Claim 13, wherein: the inner electrode layer is a grounded electrode layer and the outer electrode layers are radiofrequency electrode layers; or the inner and / or outer electrode layer or electrode layers are of the radiofrequency type and the or each radiofrequency electrode layer comprises a heat controller.
    [15]
    A process according to any of Claims 11 to 14, which process comprises depositing a polymeric coating with a thickness of 10 to 500 nm, such as from 40 to 100 nm.
    [16]
    A process according to any of Claims 11 to 15, wherein the duration of the polymer deposition process is 15 seconds to 10 minutes, such as 30 seconds to 5 minutes.
    [17]
    A process according to any one of Claims 11 to 16, wherein the uncovered printed circuit board (PCB) is placed in the polymerization chamber in such a way that: - the printed circuit board is positioned between two electrode sets, each set being positioned on opposite sides of the chamber, and wherein each electrode set comprises a plurality of radiofrequency electrode layers and / or a plurality of grounded electrode layers; and - the distance from one side of the PCB to the electrode set positioned on that side of the PCB is within 10% of the distance from the opposite side of the PCB to the electrode set positioned on that opposite side.
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    法律状态:
    优先权:
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    GB13217922|2013-12-10|
    GB1321792.2A|GB2521137A|2013-12-10|2013-12-10|Surface Coatings|
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