The present invention relates to gold electroplating solutions and methods for electroplating gold. More specifically, the invention relates to gold electroplating solutions and methods for electroplating gold onto a stainless steel surface, with possible patterning of the gold.
Gold plating of metal surfaces of electronic devices is often essential for providing reliable, low resistance electrical contact with the metal surfaces. This is particularly true of metal surfaces made of materials that naturally form an oxide passivation layer. Such materials include, for example, stainless steels.
Stainless steel is “stainless” because it forms a generally stable chromium oxide which is impervious to most chemicals. This resistance to chemical attack also makes stainless steel a challenging surface for electroplating gold and achieving good adhesion of the plated gold to the stainless steel surface.
Typically, electroplating of gold to stainless steel uses an acid/chloride solution to plate a relatively thin nickel “strike” layer onto the stainless steel. Gold is then electroplated over the nickel layer, which may also be known as a “tie” layer. This works well, so long as the nickel is completely encapsulated by the gold. However, should any nickel be exposed, for example at an edge of a photoresist defined gold/nickel pattern, then a galvanic reaction will occur when the metals come into contact with conductive solutions in subsequent processing steps, such as commonly used metal cleaning processes. The galvanic reaction corrodes the nickel layer and undercuts the gold layer. Undercutting the gold layer destroys the integrity of the patterned gold/nickel structure.
Thus, for applications requiring a patterned gold structure, it is desirable to plate the gold directly onto the stainless steel surface. What is needed is a photoresist compatible gold plating process that results in good adhesion between the gold layer and the stainless steel surface without introducing a “tie” layers susceptible to corrosion or galvanic dissolution.
Gold (I) cyanide chemistry has also been used for electroplating gold. However, gold(I) cyanide does not perform well at a low pH condition typically used for electroplating solutions for stainless steels. For example, below a pH of 4, the gold (I) cyanide complex starts to disassociate (disproportionation), such that the gold begins to precipitate and the cyanide may be released as a toxic gas. Some forms of gold (III) chloride, such as hydrogen gold (III) tetrachloride (HAuCl4), may be stable below a pH of 4. However, gold (III) chloride plating solutions do not produce an electrodeposited gold layer with good adhesion to stainless steel.
Various embodiments concern a gold electroplating solution. The gold electroplating solution includes a gold (III) cyanide compound, a chloride compound, and hydrochloric acid. The gold (III) cyanide compound is at least one of potassium gold (III) cyanide, ammonium gold (III) cyanide, and sodium gold (III) cyanide. The chloride compound is at least one of potassium chloride, ammonium chloride, and sodium chloride. In some embodiments, if the gold (III) cyanide compound is potassium gold (III) cyanide, then the chloride compound is potassium chloride; if the gold (III) cyanide compound is ammonium gold (III) cyanide, then the chloride compound is ammonium chloride; and if the gold (III) cyanide compound is sodium gold (III) cyanide, then the chloride compound is sodium chloride. In further embodiments, the gold (III) cyanide compound is potassium gold (III) cyanide and the chloride compound is potassium chloride. In some embodiments, the solution has a pH between about 0 and about 1, or between about 0.7 and about 0.9. In some embodiments, a concentration of the gold (III) cyanide compound is between about 1.0 grams of gold per liter of solution and 3.0 grams of gold per liter of solution, and a concentration of chloride anions is between about 0.30 moles per liter of solution and 0.60 moles per liter of solution. In further embodiments, the concentration of the gold (III) cyanide is between about 1.8 grams of gold per liter of solution and 2.2 grams of gold per liter of solution, and a concentration of chloride anions is between about 0.45 moles per liter of solution and 0.55 moles per liter of solution. In some embodiments, the solution is free of ethylenediamine hydrochloride, and/or oxidizing acids, including nitric acid.
Various embodiments concern methods of producing an electrodeposited gold pattern directly onto a stainless steel surface. Such methods can include creating a photoresist pattern on the stainless steel surface, cleaning portions of the stainless steel surface not covered by the photoresist pattern, immersing the stainless steel surface in a gold electroplating solution, and applying a voltage between an anode within the gold electroplating solution and the stainless steel surface to generate a current from the anode to the stainless steel surface to electroplate gold from the gold electroplating solution onto the stainless steel surface. The gold electroplating solution includes a gold (III) cyanide compound, a chloride compound, and hydrochloric acid. The gold (III) cyanide compound is at least one of potassium gold (III) cyanide, ammonium gold (III) cyanide, and sodium gold (III) cyanide. The chloride compound is at least one of potassium chloride, ammonium chloride, and sodium chloride. If the gold (III) cyanide compound is potassium gold (III) cyanide, then the chloride compound is potassium chloride; if the gold (III) cyanide compound is ammonium gold (III) cyanide, then the chloride compound is ammonium chloride, and if the gold (III) cyanide compound is sodium gold (III) cyanide, then the chloride compound is sodium chloride. In some methods the gold (III) cyanide compound is potassium gold (III) cyanide and the chloride compound is potassium chloride.
Such methods can also include adding sufficient hydrochloric acid to the gold electroplating solution such that the gold electroplating solution has a pH between about 0 and about 1, or such that the gold electroplating solution has a pH between about 0.7 and about 0.9. Such methods can also include maintaining a concentration of potassium gold (III) cyanide in the gold electroplating solution between about 1.0 grams of gold per liter of solution and 3.0 grams of gold per liter of solution, and maintaining a concentration of chloride anions in the gold electroplating solution between about 0.30 moles per liter of solution and 0.60 moles per liter of solution. Such methods can further include maintaining a concentration of potassium gold (III) cyanide in the gold electroplating solution between about 1.8 grams of gold per liter of solution and 2.2 grams of gold per liter of solution, and maintaining a concentration of chloride anions in the gold electroplating solution between about 0.45 moles per liter of solution and 0.55 moles per liter of solution.
In such methods, the voltage generates a continuous direct current, in which the continuous direct current produces a current density at the stainless steel surface of between 1 ampere per square decimeter and 40 amperes per square decimeter. In such methods, the voltage generates a pulsed direct current, and the pulsed direct current may produce a time averaged current density at the stainless steel surface of between 1 ampere per square decimeter and 40 amperes per square decimeter.
Such methods can further include cleaning the stainless steel surface with an oxygen containing plasma cleaning process. The plasma process may be in a partial vacuum, or at atmospheric pressure.
Such methods of producing an electrodeposited gold pattern directly onto a stainless steel surface may be employed for depositing gold on a stainless steel surface of a disk drive head suspension, an optical image stabilization suspension, or a medical device.
While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which describes illustrative embodiments of the invention. Accordingly, the detailed description is to be regarded as illustrative in nature and not restrictive.
While the invention is amenable to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and are described in detail below. The intention, however, is not to limit the invention to the particular embodiments described. On the contrary, the invention is intended to cover all modifications, equivalents, and alternatives falling within the scope of the invention as defined by the appended claims.
Embodiments described below enable electroplating a layer of gold directly onto a stainless steel surface. The resulting electroplated gold layer has good adhesion to the stainless steel surface without need for subsequent heat treatment, cladding pressure or other post treatment to gain needed adhesion. Some embodiments are compatible with some commercially available photoresists.
Gold may be electrodeposited directly onto a stainless steel surface by electroplating gold ions from a gold electroplating solution onto a cathodically charged stainless steel surface. For example, a gold electroplating solution may be formed by dissolving gold ions into a suitable electrolyte.
In certain embodiments, the gold ions may be from gold (III) cyanide, such as potassium gold (III) cyanide (KAu(CN)4), ammonium gold (III) cyanide (NH4Au(CN)4), sodium gold (III) cyanide (NaAu(CN)4), and combinations thereof. Suitable concentrations of the potassium gold (III) cyanide (KAu(CN)4), ammonium gold (III) cyanide (NH4Au(CN)4), or sodium gold (III) cyanide (NaAu(CN)4) include, but are not limited to, from about 1.0 grams of gold per liter of solution to about 3.0 grams of gold per liter of solution, from about 1.8 grams of gold per liter of solution to about 2.2 grams of gold per liter of solution or about 2 grams of gold per liter of solution of the gold electroplating solution.
The gold electroplating solution may also include one or more acids. A suitable acid for use in the gold electroplating solution includes hydrochloric acid (HCl). The acid may be mixed with water, such as deionized water, to control the pH of the gold electroplating solution.
The gold electroplating solution may have a low, or acidic, pH. For example, the gold electroplating solution may have a pH less than about 1 and greater than 0. More particularly, a suitable pH for the gold electroplating solution may be between about 0.7 and 0.9. In some embodiments, maintaining the gold electroplating solution at a low pH, such as at pH less than about 1, results in electrocleaning a stainless steel surface during the electrodeposition process. This electrocleaning process may eliminate passivation oxide from the stainless steel surface and may produce an electrodeposited gold layer directly on the stainless steel surface with good adhesion.
The gold electroplating solution containing the gold ions may also include potassium chloride (KCl), ammonium chloride (NH4Cl), and/or sodium chloride (NaCl). In some embodiments, the potassium chloride, ammonium chloride, or sodium chloride may be added to the gold electroplating solution to control the concentration of chloride anions with little effect on pH. For example, in some embodiments, the gold electroplating solution may have a concentration of chloride anions between about 0.30 moles per liter of solution and 0.60 moles per liter of solution. More particularly, the gold electroplating solution may have a concentration of chloride anions between about 0.45 moles per liter of solution and 0.55 moles per liter of solution.
In some embodiments, an gold electroplating solution of a gold (III) cyanide, such as potassium gold (III) cyanide (KAu(CN)4), ammonium gold (III) cyanide (NH4Au(CN)4), or sodium gold (III) cyanide (NaAu(CN)4); a chloride, such as potassium chloride (KCl) or ammonium chloride (NH4Cl); and hydrochloric acid (HCl) produce an electrodeposited gold layer directly onto a stainless steel surface with good adhesion. The gold electroplating solution is compatible with commercial photoresists, and does not produce a build-up on the electroplating anode.
Gold (III) cyanide is stable to a pH approaching 0 due to strong bond strength between the gold (III) and the cyanide. Because of this strong bond strength, gold (III) cyanide has low plating efficiency when compared, for example to gold (I) cyanide. For example, during electrodeposition within a gold electroplating solution containing gold (III) cyanide and having a pH of about 0, only approximately 30% of the reaction occurring at an electroplating surface is gold deposition. The remaining 70% involves other chemical reactions, such as hydrogen reactions with oxides on the surface, which are generally not desirable for high efficiency plating. It has been surprisingly found that in some embodiments at least some of the hydrogen reactions with oxides serve a desirable purpose when electrodepositing onto a stainless steel surface: they electroclean the stainless steel surface and may enable good or improved adhesion of the gold to the stainless steel surface.
In contrast, other forms of gold (III), such as HAuCl4, may be stable at a pH less than 4, but have a bond strength between the gold (III) and the chloride that is insufficient to favor the hydrogen reactions over the gold deposition reaction. Thus, gold GM chloride plating solutions do not produce an electrodeposited gold layer with good adhesion to stainless steel.
In some embodiments, the gold electroplating solution may be suitable for use with surfaces, such as stainless steel surfaces, that have a photoresist or other desired organic material. For example, in some embodiments, the gold electroplating solution may be free of oxidizing acids, such as nitric acid, sulfuric acid, nitrate salts or other components which may be, or which may combine, to be corrosive to organic material.
In some embodiments, the gold electroplating solution may be free of ethylenediamine hydrochloride. In some embodiments, ethylenediamine hydrochloride may be used to enhance electrical conductivity and provide the chloride ions. However, it has been found that in some embodiments, ethylenediamine can polymerize on the electroplating anode, rendering it ineffective.
In some embodiments, producing an electrodeposited gold pattern directly onto a stainless steel surface may begin with producing a photoresist pattern on the stainless steel surface of a substrate. The photoresist pattern may be produced using, for example, a negative-acting dry film photoresist. Such photoresists may be developed using an aqueous solution. After developing and optionally baking the photoresist pattern, the portion of the stainless steel surface not covered by photoresist may optionally be cleaned to remove residual organics from the portions of the stainless steel surface where gold is to be electroplated. That is, the stainless steel surface may be cleaned to remove residual organics from the portions of the stainless steel surface that are or are intended to be exposed. Cleaning to remove residual organics may be done, for example, by exposing the stainless steel surface to a brief oxygen plasma cleaning process, such as an atmospheric plasma clean or a corona clean. The oxygen plasma cleaning process may be implemented as either an inline process (e.g., continuous reel-to-reel process) or an off-line process (e.g., a panel, or piece-part process).
In some embodiments, an optional wet cleaning process may follow the plasma cleaning process. In the wet cleaning process, the stainless steel surface may be immersed in a wet cleaning solution prior to immersion in the gold electroplating solution to increase the surface energy of the stainless steel surface and promote wetting in the gold electroplating solution. The wet cleaning solution may include one or more non-oxidizing mineral or organic acids. In some embodiments, the wet cleaning solution may include hydrochloric acid or citric acid.
Following the cleaning process, one or more substrates having patterned stainless steel surfaces may be immersed in the gold electroplating solution. One or more anodes may also be immersed in the gold electroplating solution and a voltage may be applied between the anode(s) and the stainless steel surface(s) to generate a current from the anode(s) to the stainless steel surfaces(s) to electroplate gold from the gold electroplating solution onto the stainless steel surface(s).
In some embodiments, the current is a continuous direct current generated between the electrodes. In other embodiments, the form of the current may be pulsed direct current (also known as chopped direct current). In pulsed direct current, the direct current is cycled between on and off. The period of time that the current is on in an on/off cycle may be different from the period of time that the current is off in the cycle. The period of time that the current is on may range from 5% of a cycle to 50% of a cycle. The frequency of on/off cycles may be from 5 Hz to 200 Hz. The current may be cycled on and off many times to deposit gold to a desired thickness.
In some embodiments, the continuous direct current generated may have a current density at the stainless steel surface(s) of between 1 ampere per square decimeter (ASD) and 40 ASD. In other embodiments, the current density at the stainless steel surface(s) may be about 4 ASD.
In some embodiments, in which the current is a pulsed direct current, the current density is a time averaged current density at the stainless steel surface(s) of between 1 ASD and 40 ASD. In other embodiments, the time averaged current density at the stainless steel surface(S) may be about 4 ASD.
As described herein, electrocleaning of the stainless steel may occur during the electroplating process. For example, in some embodiments in which electroplating occurs at a pH of 1 or less, water disassociating at the cathodically (negatively) charged stainless steel surface creates hydrogen cations. These hydrogen cations, and/or hydrogen cations supplied by the acid content, then form hydrogen reactive neutrals which combine with the oxygen from the surface iron, nickel, and chromium oxides. The chlorides in the gold electroplating solution then may complex with the now loosely attached iron, nickel and chromium, which then get “re-electroplated” to the stainless steel surface as a metal without the oxide. Thus, in some embodiments, in addition to removing the oxide passivation layer from the surface of the stainless steel, the electrodeposition process may also keep the metals contamination levels low.
In some embodiments, the gold electroplated directly onto stainless steel has good adhesion. The adhesion may be verified by any suitable method known in the art, such as a tape test, scratch test, bend test, peel test or any other pull or shear test. A more quantifiable scratch test may be conducted by forming lines and spaces by electroplating gold to a thickness of at least 3 microns, and then running a razor blade across a group of 20 micron lines and spaces. Electroplated gold having unsuitable or bad adhesion to the stainless steel surface will peel away from the stainless steel surface. For example, the gold layer will peel away from the stainless steel surface should any voids exist between the gold and the stainless steel. Further verification of void free plating (i.e, of good or suitable adhesion) may be provided by observation of the interface between gold and stainless steel by focused ion beam.
In some embodiments, the chloride, such as potassium chloride (KCl) or ammonium chloride (NH4Cl), may add chloride ions, in addition to those supplied by the hydrochloric acid (HCl), for complexing the free iron, nickel, and chromium, as described herein. By adjusting the potassium chloride (KCl) or ammonium chloride (NH4Cl), the total chloride concentration can be adjusted independently of the pH, which is adjusted by the hydrochloric acid (HCl).
Additionally or alternatively, the potassium chloride (KCl), ammonium chloride (NH4Cl), or sodium chloride (NaCl) in combination with the acid, such as hydrochloric acid (HCl), may provide a pH buffer system and may reduce or eliminate the risk of the pH of the gold electroplating solution changing during the electroplating process.
The present invention is more particularly described in the following examples that are intended as illustration only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art.
Electroplating Test
As shown in
During each electroplating test, an electrical current flowed from the positive terminal of power source 14, through anode cable 18 to anode 16. The current the flowed from anode surface 26, through gold electroplating solution 24, to cathode surface 28 of cathode 20. Water in gold electroplating solution 24 disassociated at cathode surface 28 creating hydrogen cations and hydrogen reactive neutrals which aggressively combined with the oxygen from iron, nickel, and chromium oxides on cathode surface 28. The high level of chlorides in the gold electroplating solution 24 then complexed with the now loosely attached iron, nickel and chromium, which were then “re-electroplated” to the stainless steel of cathode surface 28 as a metal without the oxide. Once the oxide passivation layer from cathode surface 28 was removed, gold from the gold (III) cyanide in gold electroplating solution 24 plated onto to cathode surface 28. From cathode 20, the current flow returned to the negative terminal of power source 14 through cathode cable 22.
The electoplating test described above was employed in electroplating examples of varying chloride concentrations, as shown in the TABLE below. In each example, the current density across the cathode surface ranged between a high of 40 amps per square decimeter (ASD) at the proximal portion to a low of 1 ASD at the distal portion, with a nominal 3.8 ASD within the intermediate portion. In each example, the gold electroplating solution consisted of an aqueous solution of potassium gold (III) cyanide (KAu(CN)4), potassium chloride (KCl), and hydrochloric acid (HCl). KAu(CN)4 was maintained at a concentration of 2.0 g of gold per liter of solution (or about 3.5 g of KAu(CN)4 per liter of solution). HCl concentration was maintained at 0.31 M, keeping the pH of the gold electroplating solution below 1. Plating time was for 60 seconds at a temperature of 23 C.
In each example, the chloride concentration was varied by varying the concentration of KCl. The chloride concentration was reduced to examine changes in conductivity of the gold electroplating solution, as indicated by a measured electrical potential between the anode and the cathode (inter-electrode potential). The examples and results are summarized in the TABLE below.
As shown in the TABLE, variations in chloride concentration for the embodiments described had a small, but measureable change in bath conductivity, as indicated by the inter-electrode potential. In all three examples, visual inspection of the electroplated gold on the stainless steel cathode surface showed it to be smooth, shiny, and well-adhered based on scratch tests described below. This was the case across the range of current densities tested, 1 ASD to 40 ASD. Thus, as shown in the examples of the TABLE, embodiments are robust, producing good results across a wide range of conditions.
Example Structures
Direct electroplating of a gold layer directly onto an SST layer facilitates the development of advantageous gold patterns that may be used in hard disk drive suspensions. Example advantageous applications described herein are related to hard disk drive suspensions. However, the disclosure recognizes that one having skill in the art and the benefit of this disclosure may utilize the gold electroplating solution to electroplate gold directly onto SST in a variety of other suitable applications as well, for example, optical image stabilization suspension devices (such as, e.g., those of the type disclosed in PCT International Publication No. WO 2014/083318) and insertable or implantable medical devices (such as, e.g., catheters, pacemakers, defibrillators, leads and electrodes).
In contrast, the gold electroplating solution facilitates electroplating the gold layer 110 directly onto the SST layer 115 without the nickel layer 105 with the gold layer 110 being patterned by a photoresist. The gold layer 110 is directly supported by the SST layer 115, even after a metal cleaning process, which improves the edge quality and reduces the potential for flaking relative to the use of an intervening nickel layer 105. The electrodeposited and patterned gold layer 110 may be used in a variety of applications, including hard disk drive components.
Perhaps as best seen in
Turning to
As shown in the illustrated embodiment, one or more SST pads 320 have a corresponding copper bond pad 340 and one or more corresponding vias 330, which electrically couples the SST pad 320 with the corresponding copper bond pad 340. The SST pad 320 facilitates the bonding of the corresponding copper bond pad 340 during ACF bonding to the trace side of the tail 300.
Also, as shown, one or more SST pads 320 do not have a corresponding copper bond pad 340 but have a trace portion 315. For such SST pads 320 having a gold bond pad 325, however, the ACF film may be deposited onto the gold bond pad 325 for ACF bonding to the SST side of the tail 300. This structure including gold bond pads 325 on SST pads 320 allows for ACF bonding to both sides of the tail 300 without an additional process of introducing copper to the SST side of the tail 300. Furthermore, with the absence of a copper bond pad 340, this structure enables more space for the traces of the trace layer 310 to extend along the tail 300 and thus higher densities of traces and bonding areas per tail 300.
Various modifications and additions can be made to the exemplary embodiments discussed without departing from the scope of the present invention. For example, while the embodiments described above refer to particular features, the scope of this invention also includes embodiments having different combinations of features and embodiments that do not include all of the described features. Accordingly, the scope of the present invention is intended to embrace all such alternatives, modifications, and variations as fall within the scope of the claims, together with all equivalents thereof.
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Parent | 14996412 | Jan 2016 | US |
Child | 16794060 | US |