US20030226758A1 - Tin plating method - Google Patents

Tin plating method Download PDF

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US20030226758A1
US20030226758A1 US10/379,926 US37992603A US2003226758A1 US 20030226758 A1 US20030226758 A1 US 20030226758A1 US 37992603 A US37992603 A US 37992603A US 2003226758 A1 US2003226758 A1 US 2003226758A1
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tin
planes
angle
equivalent
plane
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Andre Egli
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Rohm and Haas Electronic Materials LLC
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Shipley Co LLC
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Publication of US20030226758A1 publication Critical patent/US20030226758A1/en
Priority to US11/180,952 priority patent/US8518230B2/en
Priority to US11/311,748 priority patent/US8491774B2/en
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12715—Next to Group IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12722—Next to Group VIII metal-base component

Definitions

  • the present invention relates to the field of tin and tin-alloy plating.
  • the present invention relates to the reduction of whisker formation in a tin or tin-alloy film.
  • Tin layers are typically used in the electronics industry to provide good solderability of components.
  • tin layers may be deposited on a copper lead frame to provide a solderable finish.
  • tin layers particularly electrodeposited tin layers, are subject to spontaneous whisker formation. “Whiskers” are hair-like single crystals that grow from the surface of the tin layer. Tin whiskers may range in diameter from a few nanometers to several microns (6 nanometers to 6 microns being common) and can reach lengths of several millimeters. Such whiskers can create shorts and introduce noise into electronic circuitry, thus creating a reliability problem in electronic devices.
  • tin whiskers form as a result of stresses in the tin or tin-alloy layer, although bulk diffusion of tin is also believed to be involved.
  • the precise growth mechanism of tin whiskers is not fully understood.
  • a number of stress-causing factors have been postulated, including lattice stresses due to the presence of impurity atoms in the tin layer, residual stresses due to tin plating conditions, stresses due to mechanical loading or working of the tin layer, stresses due to interaction with adjacent layers, such as intermetallic compound formation, differences in thermal expansion and the like, among others. See, for example, Ewell et al., Tin Whiskers and Passive Components: A Review of the Concerns, 18 th Capacitor and Resistor Technology Symposium , pp 222-228, March, 1998.
  • Whiskers then grow from the grain whose surface oxide is sheared, in order to release the compressive stress in the tin film.
  • Both of the above-described articles fail to provide a method for overcoming the problem of tin whisker formation.
  • U.S. Pat. No. 5,750,017 discloses a method of electrodepositing tin or tin alloy onto a metal substrate using pulse plating conditions. Such plating method provides a tin layer typically having a thickness of 3 to 6 microns wherein the grain size of the tin is from 2 to 8 microns. Although such grain size is postulated by Zhang to reduce tin whisker formation, such tin deposits still suffer from tin whisker growth.
  • tin whisker formation can be greatly reduced by providing a tin or tin-alloy film or layer in which the tin or tin-alloy layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof. Such a condition increases the tendency to whisker formation.
  • the present invention provides a method of reducing tin whisker formation that involves electrodepositing a layer of tin or tin-alloy on a substrate, wherein the tin or tin-alloy layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof.
  • the present invention provides a tin or tin-alloy layer having reduced whisker formation, wherein the tin or tin-alloy layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof.
  • tin or tin-alloy layer is electrodeposited.
  • the present invention provides an electronic device comprising a tin or tin-alloy layer, wherein the tin or tin-alloy layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof.
  • FIG. 1 is a table showing the smallest possible angle between two individual crystal planes
  • FIG. 2 is a correlation map of all possible crystal planes in a tin layer.
  • FIG. 3 is a correlation map showing the observable crystal plane orientations within a 2 ⁇ -angle of 20° to 100° from X-ray diffraction.
  • underlayer refers to a layer, preferably a metal layer, disposed between a substrate and a tin or tin-alloy layer. All amounts are percent by weight and all ratios are by weight, unless otherwise noted. All numerical ranges are inclusive and combinable in any order, except where it is obvious that such numerical ranges are constrained to add up to 100%.
  • whisker growth occurs as a stress release mechanism. From cross-sectional analysis of electroplated deposits, it is known that the grains grow normal to the substrate, forming a fiber texture. If the fibers have a diameter in the range of the deposit thickness, a well polygonized structure is observed. On the other hand, if the diameter is significantly smaller than the deposit thickness, a columnar structure is observed. It has been postulated that such columnar structure of electroplates represents an ideal situation for grain sliding. Accordingly, such grain boundaries are decisive as to whether whiskers grow or not.
  • Grain boundaries are divided into small- and large-angle grain boundaries. These angles are defined by the crystal planes between two neighboring grains. If the tilt angle between the orientations of two grains is below 15°, the resulting grain boundary is denoted to have a small-angle. Above this value, the grain boundary is denoted to have a large-angle. Diffusion rates depend largely on the grain boundary angle. Diffusion in small-angle grain boundaries approaches the values of volume diffusion, whereas diffusion in large-angle grain boundaries is orders of magnitudes faster. Naturally occurring metals are usually polycrystalline and consist, therefore, in major part of large-angle grain boundaries. The situation is very different with materials that show fibre texture. In an idealized view such a material consists only of 0° angle grain boundaries.
  • this stage corresponds most likely to a deposit where only one crystal growth orientation is observed.
  • Two things are characteristic for such a deposit: (1) the diffusion rate is very slow, and (2) the diffusion rate throughout the deposit is approximately the same. If, in contrast, the angles in a deposit are large, a fast diffusion along the grain boundaries occurs. It is clear that in the first situation, the deposit is not able to release stress from the bottom, whereas in the latter case the stress will be continuously released immediately after such stress is formed.
  • the large-angle grain boundary case corresponds to the first stage in the Lindborg model discussed above, where all diffusion processes are based on re-arrangements within the tin lattice, so-called non-conservative dislocation motions.
  • ⁇ is the angle between two planes
  • h 1 k 1 l 1 and h 2 k 2 l 2 are the Miller-indices defining the planes in the elementary cell. In this calculation all possible geometrical transformations of a given crystal plane should be considered. This is desired due to the existence of equivalent crystal planes. Such equivalent planes have the same d-line spacing resulting in the same 2 ⁇ ).
  • the tetragonal system allows the following variations: (hkl), (-hkl), (h-kl), (khl), (-khl), (k-hl), (-h-kl), (-k-hl), (hk-l), (-hk-l), (h-k-l), (kh-l), (-kh-l), (k-h-l), (-h-k-l), (-k-h-l).
  • Only small-angle grain boundaries are considered to be of interest for whisker growth.
  • the table in FIG. 1 shows only the smallest possible angle between two individual crystal planes.
  • FIG. 2 is a correlation map of all possible crystal planes in a tin deposit.
  • the correlation map of FIG. 2 was prepared using the data from FIG. 1.
  • X-ray diffraction analysis is not able to show all the crystal plane orientations shown in FIG. 2. Therefore, the correlation map must be reduced, for practical reasons, to the observable crystal plane orientations within a 20 ⁇ -angle of 20° to 100°. Such reduced correlation map is shown in FIG. 3.
  • Tin deposits with two or more adjacent crystal planes in a crystal plane orientation correlation map have the opportunity to form small-angle grain boundaries.
  • An angle likely exists where conservative and non-conservative diffusion processes find an optimum to grow whiskers.
  • grain boundaries having interplanar angles of 5° to 22° have the greatest tendency to form whiskers.
  • the 5° to 22° angle between adjacent planes also includes angles of 158° to 175° due to the tetragonal symmetry of the tin crystal.
  • the intensity of each of these is desirably less than 5% of the total intensities for observed peaks.
  • the intensity of each of these planes is desirably less than 10% of the summarized intensity of all observed peaks within the X-ray diffraction spectrum.
  • the present invention provides a method of reducing tin whisker formation by depositing a layer of tin or tin-alloy on a substrate, wherein the tin or tin-alloy layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof, as determined by X-ray diffraction analysis.
  • substantially free it is meant that the intensity of at least one of the crystal planes in each pair forming an angle of 5° to 22° is less than or equal to 15% of the total peak intensities of all observed peaks from the X-ray diffraction analysis, preferably less than or equal to 10%, and more preferably less than or equal to 5%.
  • the intensity of at least one crystal plane of each pair should not exceed 15% of the summarized peak intensities of all observed peaks, or else whisker formation may occur.
  • the not detectable (002) plane is assumed to have a non-negligible abundance.
  • Tin deposits that are substantially free of adjacent crystal planes having an angle between them of 5° to 22° may be achieved by selecting conditions and/or tin plating baths to favor a wide range of crystal planes such that the intensities of crystal planes having an angle between them of 5° to 22° are less than 15% of the total peak intensities in the X-ray diffraction spectrum.
  • plating conditions include, for example, using direct current plating and pulsed plating, including pulse periodic reverse electroplating.
  • Preferred plating baths include compounds that favor the corners of the crystal plane correlation triangle, i.e., (200), (002), and (220). If at least two different comers are combined, a significantly increased number of observed crystal planes can be achieved, thereby reducing the relative intensity ratio of the individual crystal plane pairs forming an angle of 5° to 22° to an acceptable value.
  • tin deposits may alternatively be achieved using conditions and/or tin electroplating baths that strictly favor one single growth orientation and thereby limit the abundance of, or eliminate, closely related crystal orientations which may form in the critical combinations necessary to promote whisker growth.
  • the present invention is suitable for reducing whisker formation in pure tin deposits as well as tin-alloys.
  • “Tin-alloys” refer to any metal containing tin and one or more other alloying elements, and thus includes, for example, binary alloys, ternary alloys and the like. Suitable alloying elements include, but are not limited to, bismuth, copper, silver, lead, antimony and zinc, and preferably bismuth, copper and silver.
  • a particularly suitable tin alloy is tin-copper. Such tin-copper alloys may contain, for example, from 0.5 to 10% copper, the balance being tin. Such tin-copper alloys may optionally contain small amounts of other alloying elements.
  • the concentrations of the one or more alloying elements may vary over a wide range. The range of such alloying elements is well within the ability of one skilled in the art.
  • the thickness of the tin or tin-alloy layers may vary across a wide range, depending upon the particular application. For example, when a tin or tin-alloy layer is deposited on a lead frame, it is typically from 1 to 10 microns thick.
  • the tin or tin-alloy layer may be deposited by a variety of means.
  • the tin or tin-alloy is deposited electrolytically.
  • Such electrolytic deposition may be, for example, by direct current (“DC”) or pulse plating, including pulse periodic reverse plating.
  • DC direct current
  • pulse plating including pulse periodic reverse plating.
  • the choice of the deposition technique will depend, for example, upon the particular substrate and the layer to be deposited.
  • the tin or tin-alloy plating bath is at a temperature of from about 20° to about 60° C., preferably from about 35° to 45° C.
  • the current density for the tin or tin alloy electroplating is from 1 to 50 amps/dm 2 , preferably from 5 to 30 A/dm 2 . Selection of a suitable applied current density can beneficially influence the crystallographic texture.
  • Suitable electrolytic tin or tin-alloy plating baths may be acidic or alkaline.
  • An exemplary acidic tin electroplating bath contains one or more solution soluble tin compounds, one or more acidic electrolytes, and optionally one or more additives.
  • Suitable tin compounds include, but are not limited to salts, such as tin halides, tin sulfates, tin alkane sulfonate such as tin methane sulfonate, tin aryl sulfonate such as tin phenyl sulfonate, tin phenol sulfonate and tin toluene sulfonate, tin alkanol sulfonate, and the like.
  • salts such as tin halides, tin sulfates, tin alkane sulfonate such as tin methane sulfonate, tin aryl sulfonate such as tin phenyl sulfonate, tin phenol sulfonate and tin toluene sulfonate, tin alkanol sulfonate, and the
  • the tin compound is tin sulfate, tin chloride, tin alkane sulfonate or tin aryl sulfonate, and more preferably tin sulfate or tin methane sulfonate.
  • the amount of tin compound in these electrolyte compositions is typically an amount that provides a tin content in the range of 5 to 150 g/L, preferably 30 to 80 g/L, and more preferably 40 to 60 g/l. Mixtures of tin compounds may optionally be used in an amount as described above.
  • Any acidic electrolyte that is solution soluble, is suitable for producing a stable tin electrolyte, and does not otherwise adversely affect the electrolyte composition may be used.
  • Suitable acidic electrolytes include, but are not limited to, alkane sulfonic acids, such as methane sulfonic acid, ethane sulfonic acid and propane sulfonic acid, aryl sulfonic acids, such as phenyl sulfonic acid, phenol sulfonic acid and toluene sulfonic acid, sulfuric acid, sulfamic acid, hydrochloric acid, hydrobromic acid, fluoroboric acid and mixtures thereof.
  • alkane sulfonic acids such as methane sulfonic acid, ethane sulfonic acid and propane sulfonic acid
  • aryl sulfonic acids such as phenyl sulfonic acid, phenol sulfonic acid and
  • the amount of acidic electrolyte is in the range of from 10 to 400 g/L, preferably from 50 to 400 g/L, and more preferably from 150 to 300 g/L. It is preferred that when the tin compound is a halide, the acidic electrolyte is the corresponding acid. For example, when tin chloride is used in the present invention, it is preferred that the acidic electrolyte is hydrochloric acid.
  • one or more alloying metal compound is used in addition to tin.
  • Suitable other metals include, but are not limited to, lead, nickel, copper, bismuth, zinc, silver, antimony, indium and the like.
  • a particularly suitable tin-alloy is tin-copper.
  • the other metal compounds useful in the present invention are any which provide the metal to the electrolyte composition in a soluble form.
  • the metal compounds include, but are not limited to, salts, such as metal halides, metal sulfates, metal alkane sulfonates, such as metal methane sulfonate, metal aryl sulfonates, such as metal phenyl sulfonate and metal toluene sulfonate, metal alkanol sulfonates, and the like.
  • salts such as metal halides, metal sulfates, metal alkane sulfonates, such as metal methane sulfonate, metal aryl sulfonates, such as metal phenyl sulfonate and metal toluene sulfonate, metal alkanol sulfonates, and the like.
  • salts such as metal halides, metal sulfates, metal alkane sulfonates, such as metal methane sulfonate, metal aryl sulfonates
  • one or more crystal plane orientation enhancing compounds can be used that act in a way to “pull” the crystal plane orientations into a favorable range in which angles of 5° to 22° between crystal planes are minimized.
  • Suitable compounds include, for example, imides, imines, such as carboxymethylated polyethyleneimine, amides, polyamides, amines, such as 3-ethyl amine, polyamines, polycarboxylates, polyols, thiols, such as dibutyl thiourea, allyl thiourea, tetramethyl thiourea, thiourea, amino thiazole, rhodanine, and sulfosalicylic acid, multi-ring compounds containing carbonyl and/or imide functionality, such as rosolic acid, isatin, and carmine, and sulfamides, such as saccharin.
  • the use of such compounds can beneficially maintain the desired crystal structure over a wide range of operating
  • additives may be used in the tin or tin alloy electroplating baths, such as reducing agents, grain refiners such as hydroxy aromatic compounds and other wetting agents, brightening agents, antioxidants, and the like. Mixtures of additives may also be used in the present invention. Such additives are useful, for example, in enhancing the efficiency and/or quality of the plating
  • Reducing agents may be added to the tin and tin-alloy electrolyte compositions to assist in keeping the tin in a soluble, divalent state.
  • Suitable reducing agents include, but are not limited to, hydroquinone and hydroxylated aromatic compounds, such as resorcinol, catechol, and the like.
  • Suitable reducing agents are those disclosed, for example, in U.S. Pat. No. 4,871,429. The amount of such reducing agent is typically from 0.1 g/L to 5 g/L.
  • Bright deposits may be obtained by adding brighteners to the tin and tin-alloy electrolyte compositions.
  • Such brighteners are well known to those skilled in the art. Suitable brighteners include, but are not limited to, aromatic aldehydes such as naphthaldehyde. benzaldehyde, allylbenzaldehyde, methoxybenzaldehyde and chlorobenzaldehyde, derivatives of aromatic aldehydes, such as benzyl acetone and benzylidine acetone, aliphatic aldehydes, such as acetaldehyde or glutaraldehyde, and acids such as acrylic acid, methacrylic acid and picolinic acid.
  • brighteners are used at an amount of 0.1 to 3 g/L, and preferably 0.5 to 2 g/L.
  • Suitable non-ionic surfactants or wetting agents include, but are not limited to, relatively low molecular weight ethylene oxide (“EO”) derivatives of aliphatic alcohols containing one or more alkyl group of up to 7 carbons or ethylene oxide derivatives of aromatic alcohols having up to two aromatic rings, which may be fused and which may be substituted with an alkyl group having up to 6 carbons.
  • the aliphatic alcohols may be saturated or unsaturated.
  • the aromatic alcohols typically have up to 20 carbon atoms prior to derivatization with ethylene oxide.
  • Such aliphatic and aromatic alcohols may be further substituted, for example, with sulfate or sulfonate groups.
  • Suitable wetting agents include, but are not limited to, ethoxylated polystyrenated phenol containing 12 moles of EO, ethoxylated butanol containing 5 moles of EO, ethoxylated butanol containing 16 moles of EO, ethoxylated butanol containing 8 moles of EO, ethoxylated octanol containing 12 moles of EO, ethoxylated octylphenol containing 12 moles of EO, ethoxylated/propoxylated butanol, ethylene oxide/propylene oxide block copolymers, ethoxylated beta-naphthol containing 8 or 13 moles of EO, ethoxylated beta-naphthol containing 10 moles of EO, ethoxylated bisphenol A containing 10 moles of EO, ethoxylated bisphenol A containing 13 moles of EO, sul
  • hydroxy aromatic compounds or other wetting agents may be added to these electrolyte compositions to provide further grain refinement. Such grain refiners may be added to further improve deposit appearance and operating current density range.
  • Suitable other wetting agents include, but are not limited to, alkoxylates, such as the polyethoxylated amines JEFFAMINE T-403 or TRITON RW, sulfated alkyl ethoxylates, such as TRITON QS-15, and gelatin or gelatin derivatives.
  • an antioxidant compound can be employed in the electrolyte composition to minimize or prevent stannous tin oxidation from occurring, for example, from the divalent to tetravalent state.
  • Suitable antioxidant compounds include, for example, dihydroxybenzene and multivalent compounds based on the elements of groups IV B, V B, and VI B in the Periodic Table of the Elements, such as those of vanadium, niobium, tantalum, titanium, zirconium and tungsten.
  • such antioxidant compounds are present in the electrolyte composition in an amount of from 0 to 2 g/l.
  • Whisker formation can be reduced or eliminated when a tin layer is deposited on any substrate, provided that the tin layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof, as determined from X-ray diffraction analysis. It is preferred that the tin or tin-alloy layer is deposited on a conductive substrate. Particularly suitable substrates include, but are not limited to, copper, nickel, nickel-alloys, cobalt, cobalt-alloys and the like.
  • the tin layer of the present invention can optionally be deposited on one or more underlayer.
  • Suitable underlayer materials include, but are not limited to, nickel, cobalt and alloys thereof.
  • nickel-alloy is meant any metal containing nickel and one or more different alloying elements, and thus includes binary alloys, ternary alloys and the like.
  • cobalt-alloy is meant any metal containing cobalt and one or more different alloying elements, and thus includes binary alloys, ternary alloys and the like.
  • Suitable alloying elements include, but are not limited to, tungsten, nickel, cobalt, phosphorus, and the like.
  • nickel in a nickel-alloy and cobalt in a cobalt-alloy varies over a wide range and is well within the ability of one skilled in the art.
  • Particularly suitable underlayers include nickel, cobalt, nickel-cobalt, nickel-phosphorus and nickel-tungsten.
  • nickel-phosphorus-alloys include those having from 2 to 13% phosphorus.
  • the minimum thickness of the underlayer is that thickness necessary to provide a substantially continuous metal layer over the substrate surface, such that the tin or tin alloy layer does not intimately contact the substrate surface.
  • a typical minimum thickness of the present underlayer is 0.05 micron.
  • suitable ranges of thickness of the underlayer are from 0.05 to 1 micron, preferably from 0.05 to 0.95 micron, more preferably from 0.1 to 0.75 micron and still more preferably from 0.1 to 0.5 micron.
  • the underlayer may be deposited by a variety of methods. Suitable methods include, but are not limited to, electroless plating, electrolytic plating, immersion plating or vapor deposition such as physical vapor deposition or chemical vapor deposition. It is preferred that the underlayer is deposited by electroless plating or electrolytic plating, with electrolytic plating being preferred. Such electrolytic deposition may be, for example, by DC or pulse plating. The choice of the deposition technique will depend upon the particular substrate and the layer to be deposited. Such choice is well within the ability of one skilled in the art.
  • a wide variety of electrolytic nickel baths may be used.
  • Such nickel baths are well known to those skilled in the art and typically contain one or more soluble sources of nickel compounds, such as nickel halides, for example, nickel chloride, nickel sulfate, nickel sulfamate, nickel fluoborate and mixtures thereof.
  • nickel compounds are typically employed in concentrations sufficient to provide nickel in the electroplating solutions in concentrations ranging from about 10 to 250 g/L. It is preferred that the nickel electroplating bath contains nickel chloride and nickel sulfamate. It is further preferred that the amount of nickel chloride in the bath is from 8 to 15 g/L and the amount of nickel as nickel sulfamate is from 80 to 150 g/L.
  • Suitable nickel plating baths typically contain one or more acids, such as boric acid, phosphoric acid, phosphorus acid and mixtures thereof.
  • Exemplary boric acid-containing nickel electroplating baths contain from 30 to 60 g/L of boric acid, and preferably about 45 g/L.
  • the pH of such baths is from about 3.0 to about 5.0, and preferably is about 4.0.
  • the operating temperature of such nickel electroplating baths may range from about 40° to about 70° C., and is preferably from 50° to 65° C.
  • the average cathode current density typically ranges from about 0.5 to 12 amperes per square decimeter, with 3 to 6 amperes per square decimeter being preferred.
  • one or more other alloying metal compound is used with the nickel.
  • Such alloying metal compounds are any which provide the metal to the electrolyte composition in a soluble form.
  • the metal compounds include, but are not limited to, salts, such as metal halides, metal sulfates, metal alkane sulfonates such as metal methane sulfonate, metal aryl sulfonates, such as metal phenyl sulfonate and metal toluene sulfonate, metal alkanol sulfonates, and the like.
  • salts such as metal halides, metal sulfates, metal alkane sulfonates such as metal methane sulfonate, metal aryl sulfonates, such as metal phenyl sulfonate and metal toluene sulfonate, metal alkanol sulfonates, and the like.
  • additives may be used in the nickel electroplating baths, such as grain refiners, wetting agents, brightening agents and the like. Mixtures of additives may also be used in the present invention. Such additives are useful in enhancing the efficiency and/or quality of the plating.
  • the present invention also provides a method of depositing a tin or tin-alloy layer on a substrate.
  • the method involves steps of depositing a tin or tin-alloy layer, wherein the tin or tin-alloy layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof, as determined from X-ray diffraction analysis.
  • the substrate includes one or more metal that forms an intermetallic compound with tin.
  • Suitable substrates include, but are not limited to, copper and alloys thereof, and brass. It is preferred that the substrate includes a copper or copper-alloy layer. Such copper alloys may contain small amounts of one or more other alloying elements.
  • the present invention further provides a substrate including a tin or tin-alloy layer wherein the tin or tin-alloy layer is substantially free of crystal planes or equivalent planes thereof forming an angle of 5° to 22° with an adjacent crystal plane or an equivalent plane thereof, as determined from X-ray diffraction analysis.
  • the present invention is particularly suitable for depositing a tin or tin-alloy layer on an electronic device substrate.
  • Suitable electronic device substrates include, but are not limited to, printed wiring board substrates, lead frames, semiconductor packages, components, connectors, contacts, chip capacitors, chip resistors and the like.
  • the present invention still further provides an electronic device including a tin or tin-alloy layer wherein the tin or tin-alloy layer is substantially free of crystal planes close together having an angle between them of 5° to 22°, as determined from X-ray diffraction analysis.
  • the present invention is particularly useful for the manufacture of tin and tin-alloy plated lead frames.
  • a particularly suitable tin-alloy for use on such electronic devices is tin-copper, however other tin alloys may also be suitably used.
  • the present invention allows for whisker formation in tin and tin-alloys to be reduced or even eliminated.
  • a plating bath is prepared by combining 50 g/L tin as tin(II) methane sulfonate, 160 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, and 5 g/L ethoxylated bisphenol A.
  • a copper substrate is electroplated in the bath at a temperature of 40° C. and a current density of 20 A/dm 2 using direct current plating.
  • X-ray diffraction analysis is conducted on the plated sample for a 2 ⁇ -angle of 20° to 100° using a Phillips X-ray diffraction instrument.
  • Example 1 The procedure described in Example 1 is repeated, except using a plating bath prepared by combining 40 g/L tin as tin(II) methane sulfonate, 200 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, and 5 g/L ethoxylated bisphenol A.
  • a plating bath prepared by combining 40 g/L tin as tin(II) methane sulfonate, 200 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, and 5 g/L ethoxylated bisphenol A.
  • Example 1 The procedure described in Example 1 is repeated, except using a plating bath prepared by combining 60 g/L tin as tin(II) methane sulfonate, 240 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 13 moles EO, and 5 g/L ethoxylated bisphenol A.
  • a plating bath prepared by combining 60 g/L tin as tin(II) methane sulfonate, 240 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 13 moles EO, and 5 g/L ethoxylated bisphenol A.
  • Example 1 The procedure described in Example 1 is repeated, except using a plating bath prepared by combining 50 g/L tin as tin(II) methane sulfonate, 260 g/L free ethane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 13 moles EO, and 5 g/L ethoxylated bisphenol A.
  • a plating bath prepared by combining 50 g/L tin as tin(II) methane sulfonate, 260 g/L free ethane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 13 moles EO, and 5 g/L ethoxylated bisphenol A.
  • Example 1 The procedure described in Example 1 is repeated, except using a plating bath prepared by combining 50 g/L tin as tin(II) phenyl sulfonate, 250 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, and 5 g/L ethoxylated bisphenol A.
  • a plating bath prepared by combining 50 g/L tin as tin(II) phenyl sulfonate, 250 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, and 5 g/L ethoxylated bisphenol A.
  • Example 1 The procedure described in Example 1 is repeated, except using a plating bath prepared by combining 50 g/L tin as tin(II) phenyl sulfonate, 250 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, and 5 g/L ethoxylated bisphenol A.
  • a plating bath prepared by combining 50 g/L tin as tin(II) phenyl sulfonate, 250 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, and 5 g/L ethoxylated bisphenol A.
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 50 g/L tin as tin(II) methane sulfonate, 160 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 13 moles EO, 5 g/L ethoxylated bisphenol A, and 5 g/L of a carboxymethylated polyethyleneimine.
  • a tin plating bath prepared by combining 50 g/L tin as tin(II) methane sulfonate, 160 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 13 moles EO, 5 g/L ethoxylated bisphenol A, and 5 g/L of a carboxymethylated polyethyleneimine.
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate, 280 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, 5 g/L ethoxylated bisphenol A; 5 g/L of a carboxymethylated polyethyleneimine; and 5 g/L thiourea.
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 50 g/L tin as tin(II) methane sulfonate, 160 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, 5 g/L ethoxylated bisphenol A, 5 g/L of a carboxymethylated polyethyleneimine, and 1 g/L dihydroxybenzene antioxidant.
  • a tin plating bath prepared by combining 50 g/L tin as tin(II) methane sulfonate, 160 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, 5 g/L ethoxylated bisphenol A, 5 g/L of a carboxymethylated polyethyleneimine,
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 55 g/L tin as tin(II) methane sulfonate, 200 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, 5 g/L ethoxylated bisphenol A, 5 g/L of a carboxymethylated polyethyleneimine, and 1 g/L vanadium pentoxide.
  • a tin plating bath prepared by combining 55 g/L tin as tin(II) methane sulfonate, 200 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, 5 g/L ethoxylated bisphenol A, 5 g/L of a carboxymethylated polyethyleneimine
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate, 5 g/l bismuth (III) as bismuth methane sulfonate, 160 g/L free methane sulfonic acid, 25 g/L ethoxylated beta-naphthol containing 8 moles EO, 5 g/L ethoxylated bisphenol A, 5 g/L of a carboxymethylated polyethyleneimine, and 1 g/L vanadium sulfate.
  • a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate, 5 g/l bismuth (III) as bismuth methane sulfonate, 160 g/L free methane sulfonic acid, 25 g/L e
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate, 1 g/L Cu as copper (II) methane sulfonate, 160 g/L free methane sulfonic acid, 30 g/L polyalkoxylated butanol, and 3 g/L of tetramethyl thiourea.
  • a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate, 1 g/L Cu as copper (II) methane sulfonate, 160 g/L free methane sulfonic acid, 30 g/L polyalkoxylated butanol, and 3 g/L of tetramethyl thiourea.
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate; 160 g/L free methane sulfonic acid, 30 g/L polyalkoxylated butanol, and 0.05 g/L of rhodanine.
  • a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate; 160 g/L free methane sulfonic acid, 30 g/L polyalkoxylated butanol, and 0.05 g/L of rhodanine.
  • Example 1 The procedure described in Example 1 is repeated, except using a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate; 160 g/L free methane sulfonic acid, 30 g/L polyalkoxylated butanol, and 3 g/L of sulfosalicylic acid.
  • a tin plating bath prepared by combining 45 g/L tin as tin(II) methane sulfonate; 160 g/L free methane sulfonic acid, 30 g/L polyalkoxylated butanol, and 3 g/L of sulfosalicylic acid.
  • the same procedures described above in Examples 1-14 are repeated, except a 0.25 micron nickel underlayer is deposited on the copper substrate prior to tin plating.
  • the plating bath contains 120 g/L of nickel sulfomate, 11 g/L of nickel chloride, and 45 g/L boric acid and has a pH of 4.0.
  • the bath temperature is 60° C. and the average cathode current density is 3 A/dm 2 .
  • Samples of etched lead frames made from a copper-rich alloy are electroplated with tin to a thickness of 10 ⁇ m using the procedures described in Examples 1-14. No barrier layers or undercoats are used.
  • the lead frames are analyzed for the presence of whiskers by scanning electron microscopy (SEM) after plating.
  • SEM scanning electron microscopy
  • the remaining plated lead frames from each set of samples are stored under controlled conditions in a test chamber at 52° C. and 98% relative humidity.
  • One sample from each Example is removed from the test chamber at one month intervals and analyzed by SEM for the presence of whiskers. It is expected that the results from the SEM analyses would show that the tin layers are substantially whisker free.

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TWI287051B (en) 2007-09-21
JP4897187B2 (ja) 2012-03-14
EP1342816A3 (en) 2006-05-24
CN1309874C (zh) 2007-04-11
US8491774B2 (en) 2013-07-23
EP1342816A2 (en) 2003-09-10
CN1458304A (zh) 2003-11-26
KR20030074215A (ko) 2003-09-19
TW200401849A (en) 2004-02-01
KR100950059B1 (ko) 2010-03-29
JP2004124249A (ja) 2004-04-22
US8518230B2 (en) 2013-08-27
US20060090819A1 (en) 2006-05-04

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