Patent Application
20240287698
The invention is directed to the use of electrolytic bronze deposits as substitutes for the noble metal electroplating in outer contact surfaces of electronic components, e.g. for use in electronic payment cards and identity cards. The invention also relates to a novel layer sequence of bronze layers.
The electrolytic deposition of brass (Cu—Zn alloy) and bronzes (Cu—Sn alloy) on consumer or decorative goods is well known (Praktische Galvanotechnik (Practical Electroplating), Eugen G. Leuze Verlag KG, 7th edition 2013, p. 261 et seq.). Among other things, they serve as a substitute for nickel-containing finishing layers and are applied to corresponding substrates at low cost, for example, in electroplating drum or rack coating methods.
In the deposition of brass and bronze layers, the solderability and, if applicable, their mechanical adhesion are critical properties that these producing layers have to exhibit. In electronic applications, the appearance of the layers is generally less important than their functionality. For the production of bronze or brass coatings on consumer goods, e.g. electronic payment cards, on the other hand, the decorative effect is also an important target parameter, in addition to the surface robustness and long durability of the coating while maintaining an appearance that is as unchanged as possible.
The deposition of a ternary alloy consisting of copper, tin and zinc is sufficiently known to the person skilled in the art. Deposition from a cyanide-free electrolyte is explained, for example, in EP 2116634. There, in addition to a high concentration of pyrophosphate anions in the electrolyte, a special reaction product of hexamethylenetetramines and epichlorohydrin is also used when the pH of the electrolyte is almost neutral. US20010014407 mentions in passing the deposition of a ternary alloy of Cu/Sn/Zn on copper surfaces as corrosion protection.
From US20100147696 it is known to deposit Cu—Zn—Sn alloy from electrolytes containing phosphonic acid. The deposits described therein give white coatings, which are, however, relatively low in zinc.
A cyanide-free, pyrophosphate-containing electrolyte for the deposition of ternary copper-zinc-tin alloys is described in Thin Solid Films, 517 (2009) 2511-2514. In this case, a layer not defined in detail is deposited from an alkaline electrolyte having the metals copper in the +2 oxidation state, zinc in the +2 oxidation state and tin in the +4 oxidation state.
EP 2037006 describes the electrolytic deposition of copper-tin-zinc alloys in a very specific atomic ratio to one another. The deposited layers have a composition which is intended to be close to the formula Cu2ZnSn. The layers thus obtained can serve as the basis for producing kesterite (CZTS or Cu2ZnSn(S,Se)4), which is a promising material for producing photovoltaically active modules (Solar Energy Materials & Solar Cells 2011, 95, 2136-2140; Chemical Physics Letters 2011, 501, 619-622).
A leadframe is a carrier for semiconductors in the shape of a stamped strip. It is a solderable, metal lead carrier in the form of a frame or comb for automatic production of semiconductor chips or other electronic components. Aside from the chip carrier, the connecting pins of the future component are also integrated into the leadframe. Chips are die-bonded onto the leadframe. The contact surfaces of the chips are connected to the connecting pins via wire bonds. After the bonding, the leadframe is extrusion-coated with a thermosetting plastic. The connecting pins extend from the plastic housing and are subsequently cut and formed. (https://ts.kurtzersa.com/electronics-production-equipment/solderlexicon/begriff/leadframe-1.html). Leadframes are therefore the metal structures inside a chip package that transmit signals from the chip to the outside (https://en.wikipedia.org/wiki/Lead_frame). In addition, the term “leadframe” also refers to the shape of the microchips produced with leadframes, i.e. the shapes with (protruding) connections. Leadframes are mounted on an insulating carrier or in a package. If the contacts are mechanically fixed, they can be separated from one another. Leadframes are stamped, but can also be laser-cut for smaller quantities. They are used, for example, in smart cards or chip cards.
Smart cards, chip cards or integrated circuit cards are typically plastic cards that have a chip on their surface. These smart cards are known from ID cards, credit cards and the like. The integrated chip is controlled via various metal surfaces which establish contact with an external read/write device. An introduction can be found here: https://en.wikipedia.orq/w/index.php?title=Smart card&oldid=1009449492.
The contacts and metal surfaces mentioned above must be able to produce contact with the read/write device under very different ambient conditions. For instance, corrosive liquids must not affect the conductivity of the metal surfaces. Ideally, their external look and feel is also not negatively affected. For these reasons, very noble metals such as gold and palladium have been used in metal surfaces to date. Usually, the noble metal layers in these applications are deposited on other metal surfaces, in particular copper and nickel.
The use of expensive noble metals makes the leadframes or smart cards themselves expensive. It would therefore be an important and innovative step forward if the layers containing noble metals in the metal surfaces on these products could be substituted by less expensive but equally resistant, visually attractive metal surfaces.
These and further objects arising from the prior art for the person skilled in the art are achieved by the use according to the present independent claims 1 and 4, respectively. Preferred embodiments are illustrated in dependent claims 2 and 3 or 5 and 6.
By using electrolytically deposited bronze layers as layer substitutes as layer substitutes for galvanically deposited noble metal layers in outer contact surfaces of electronic components such as leadframes, wherein the layer has the following composition:
Advantageous embodiments contain the following compositions in the tin-rich bronze:
Advantageous embodiments contain the following compositions in the copper-rich bronze:
Outer contact surfaces of electronic components such as leadframes are found in many products. Due to the rapid development of electronics in recent decades, semiconductors and leadframes have become essential components in almost every industry—in particular in automotive engineering. The power electronics required in electric and hybrid vehicles is just one example of how ubiquitous electronic systems are in industrial products in other industries. The person skilled in the art is aware of the other areas of application that can be considered in this respect. In particular, these leadframes are found in smart cards. Here, as stated previously, they are used to be able to connect a chip to a read/write device via a metal surface attached to the smart card. It is therefore advantageous to use bronze layers in particular for this application.
According to the present invention, the bronze layer is applied to conductive substrates. The latter are immersed as a cathode in a bronze electrolyte and a current flow is established between the cathode and anode via an anode that is also in contact with the electrolyte. A person skilled in the art knows how to proceed here. Preferably, the bronze layer can be deposited in such a way on an underlayer selected from the group consisting of Cu, Ni, nickel-phosphorus, Pd, PdNi, Au and platinum. In a particularly preferred embodiment, the bronze layer may be deposited on a copper or nickel underlayer. A preferred layer sequence in the field of the use according to the invention consists of a metal, preferably copper, underlayer followed by a nickel layer and the bronze layer(s).
In a first step, the underlayer can be cleaned and etched. The person skilled in the art knows how to proceed here (Praktische Galvanotechnik (Practical Electroplating), Eugen G. Leuze Verlag KG, 7th edition of 2013, page 167 et seq.). Subsequently, a nickel layer is preferably applied to the underlayer. This ensures that the corrosion resistance of the overall system is improved. Here, too, the person skilled in the art is guided by sufficiently well-known procedures (https://de.wikipedia.orq/w/index.php?title=Galvanisch Nickel&oldid=206755991). After another cleaning step, the first bronze layer is applied to the nickel layer. If an upper layer with a white appearance is desired, a bronze electrolyte is selected which allows a tin-rich bronze to be deposited as mentioned above. This top layer looks very similar to a palladium layer. If, however, the surface is to look more like gold, a copper-rich bronze alloy is deposited from a corresponding electrolyte. An electrolyte that can preferably be used for these purposes can be found in the following disclosed patent applications: EP1961840A1, EP2116634A1, EP2310558A1, EP2606164A1, DE102011121799A1, DE102011121798A1. Corresponding electrolytes are also commercially available, e.g. from Umicore Galvanotechnik GmbH under the name Miralloy® 2841 HS as a palladium substitute and Miralloy® 2847 1N HS as a gold substitute.
For the bronze electrolytes used, the colors of the respective surfaces can be decisively influenced by the choice of deposition parameters. For a bronze electrolyte leading to a white deposition, a tin-rich bronze electrolyte, such as Miralloy® 2841 HS, is preferably used. A high temperature during deposition, too high tin contents or a too high cyanide content in the electrolyte leads to a somewhat grayish deposition. High current densities or copper contents in the electrolyte as well as too high a pH value result in more yellowish deposits. Here, it is a matter for the person skilled in the art to select the suitable parameters in such a way that a deposition acceptable to him or her is produced. For a bronze electrolyte that leads to a golden yellow deposition, a bronze electrolyte richer in copper, such as Miralloy® 2847 1N HS, is preferably used. A high temperature during deposition, too high tin contents or a too high cyanide content in the electrolyte leads to a somewhat whitish, grayish deposition. High current densities or copper contents in the electrolyte as well as too high a pH value result in reddish depositions. Here, it is a matter for the person skilled in the art to select the suitable parameters in such a way that a deposition acceptable to him or her is produced.
With regard to the color of the bronze layers substituting the palladium (white) or gold (yellow) layer, it should be noted that they can be characterized in the Cielab system as follows. The deposited white (tin-rich) bronze metal layer advantageously has an L* value of over +84. The a* value is preferably −0.2 to 0.25 and the b* value between +2 and +4, according to the Cielab color system (EN ISO 11664-4—latest version as of the filing date). The values were determined with a Konica Minolta CM-700d. The deposited yellow (copper-rich) bronze layer advantageously has an L* value of over +97. The a* value is preferably −0.2 to 0.2 and the b* value between +2 and +4, according to the Cielab color system (EN ISO 11664-4—latest version as of the filing date). The values were determined with a Konica Minolta CM-700d.
The nickel underlayer mentioned above can be produced by a person skilled in the art (e.g. DE102018133244A1 and the literature cited therein). Preferably, such a nickel layer originates from a nickel sulfamate electrolyte. A bath for the deposition of nickel that has been known for a long time and is still in use today in a variety of modified forms is the nickel sulfamate bath with its basic components of 300-450 g/l nickel sulfamate, 0-30 g/L nickel chloride and 30-45 g/L boric acid (Praktische Galvanotechnik (Practical Electroplating), Eugen G. Leuze Verlag KG, 7th edition 2013, p. 272 et seq.). Others are commercially available, e.g. from Umicore Galvanotechnik GmbH under the name NIPHOS® 964 or NIPHOS® 964 HS, as well as e.g. here: https://www.microchemicals.com/de/produkte/galvanik/nickel_elektrolytnb_s emiplate_ni_100.html. The thickness of the nickel layer is to be determined by the person skilled in the art and should be between 2-4, preferably between 2.5-3.5 and very preferably between 2.75-3.25 μm for this application.
The thickness of the bronze layers can also be set by the person skilled in the art according to his or her preferences. The white-looking bronze layer, which is considered a palladium substitute, preferably has a thickness of 0.1-2 μm, preferably 0.2-1 μm and very preferably 0.3-0.7 μm. The yellow-looking bronze layer, which is considered a gold substitute, preferably has a thickness of 0.1-2 μm, preferably 0.2-1 μm and very preferably 0.3-0.7 μm.
The present invention also relates to an advantageous layer sequence of at least one electrically conductive underlayer, a first bronze layer and a second bronze layer which differs from the first, at least in composition. Accordingly, the invention comprises a layer sequence having a metal underlayer and two successive, electrolytically deposited bronze layers, wherein one of these two layers has the following composition: Cu 45-60%, Sn 30-50% and Zn 5-15% (in each case relative to the bronze layer);
Depending on which surface color is desired, the tin-rich or the copper-rich bronze layer can form the final surface layer. Preferably, the surface layer is the one with the more copper-rich, i.e., yellowish, alloy. For the depositions of the layers or underlayers, the statements made above about the use apply accordingly. The underlayers can also be selected and established by the person skilled in the art in accordance with the statements made above. For the thicknesses of the bronze layers, reference is also made to the statements made above. The bronze layers generally form the uppermost layers of the contact material. Finally, they are advantageously provided only with a transparent organic protective film, which is known to the person skilled in the art as anti-tarnish protection, topcoat and/or passivation. The person skilled in the art knows how to perform these steps (Praktische Galvanotechnik (Practical Electroplating), Leuze Verlag, 7th edition of 2013, page 167 et seq.). The application of anti-tarnish protection is a protective process for decorative noble metals, for example. This completely transparent layer in the nanometer range protects the base material from oxidation, discoloration and mechanical stress. The color and gloss are not affected. The coating is chemically resistant, dirt and water repellent and has a long service life.
The bronze layers presented here can easily substitute correspondingly more expensive noble metal surface layers without any problems, at least for the specified application. This leads to a drastic reduction in the cost of use, since noble metals are correspondingly expensive. In particular, gold and palladium surfaces can be advantageously substituted in this way. In tests, the present invention has proved surprisingly advantageous. Table 1 below shows corresponding tests and the results of a layer sequence according to the invention, as just mentioned, in comparison with standard gold or palladium surfaces. Compared to gold or palladium, the bronze depositions offer lower scratch sensitivity, comparable resistance in the required corrosion tests and an almost identical appearance.
In order to detect the susceptibility of a coating or the entire layer structure to corrosion, the 4-component noxious gas test was used for testing.
The 4-component noxious gas test (EN 60068-2-60) consisting of SO2, NO2, Cl2, H2S, which is also performed in a special noxious gas air conditioning system.
The Pressure Cooker Storage Test (https://storage.googleapis.com/verasol-assets/Global-LEAP-EPC-Test-Method_v1.pdf) is a delamination test usually performed on printed circuit board products at high pressure and temperature. Outgassing from the deposited layers, which can lead to delamination of the deposited layers, is also detected with this test.
From the list in Table 1, it is apparent that the lower-cost bronze layers can certainly substitute the noble metal layers without causing any adverse effects for use in the area of application under consideration here. This was by no means to be expected on the priority date.
The following methods have been found to be particularly successful in connection with the present invention:
The following layers were electrolytically applied to a polyimide foil laminated pre-structured copper foil:
The person skilled in the art will proceed with the above embodiment as shown in
It is advantageous that steps for electrolytic cleaning, degreasing, rinsing and activation of the respective base for deposition are included in the deposition of the layer sequence according to the invention. Thus, the preparation steps in the method step just mentioned can comprise these activities. Preferably, the preparation for the next electrolytic step is as follows:
According to the invention, the term “electrolytic” means that the process is carried out using external power sources (e.g. electrolytically).
Further information on execution:
For pre-cleaning; acid cleaner, e.g. Umicore Cleaner 865, from Umicore Galvanotechnik (https://ep.umicore.com/storage/ep/umicoregt-list-of-products-april-2021.pdf)
For copper activation: copper micro etchants;
Further components according to manufacturer's instructions as per instruction sheet.
To produce the adhesion-promoting nickel layer:
For alkaline cleaning, e.g. Umicore Cleaner 6032, from Umicore Galvanotechnik (https://ep.umicore.com/storage/ep/umicoregt-list-of-products-april-2021.pdf)
Further components according to manufacturer's instructions as per instruction sheet.
Method for applying a bronze layer as a gold or palladium substitute
The following methods:
To produce a bronze layer similar to gold, e.g. MIRALLOY® 2847 1N HS, Umicore Galvanotechnik (https://ep.umicore.com/storage/ep/umicoregt-list-of-products-april-2021.pdf)
Further components according to manufacturer's instructions as per instruction sheet.
To produce a bronze layer similar to palladium, e.g. MIRALLOY® 2841 HS, from Umicore Galvanotechnik (https://ep.umicore.com/storage/ep/umicoregt-list-of-products-april-2021.pdf)
Further components according to manufacturer's instructions as per instruction sheet.
For alkaline cleaning, e.g. Umicore Cleaner 6032, from Umicore Galvanotechnik (https://ep.umicore.com/storage/ep/umicoregt-list-of-products-april-2021.pdf)
Further components according to manufacturer's instructions as per instruction sheet.
Method for applying passivation, anti-tarnish protection or topcoat, e.g. Umicore Sealing 692 EL (https://ep.umicore.com/storage/ep/umicoregt-list-of-products-april-2021.pdf)
Further components according to manufacturer's instructions as per instruction sheet.
The method steps between the individual process steps are generally rinsing processes with water of appropriate quality.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2021 117 095.8 | Jul 2021 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/068007 | 6/30/2022 | WO |
