Improved electroless copper deposition

Abstract: The invention concerns a process for the formation of an electroless copper deposit from a plating bath comprising an aqueous solution containing a copper compound, a complexing agent for copper, a reducing agent for copper, a pH-adjusting agent, an additive selected from the group consisting of soluble inorganic silicon compounds and soluble inorganic germanium compounds, and in which process an oxygen containing gas is injected into the solution. Electrolessly deposited copper with improved properties of smoothness and elongation is obtained by controlling one or more of the plating bath parameters pH, complexing agents, sources of iron so as to limit the content of trace iron in the deposited copper layer to a value below 1.5 mg per mole of copper. Printed wiring boards manufactured in accordance with the invention display improved resistance to thermal stress and thermal cycling of copper plated-through holes. The achieved improvements are enhanced by the addition of vanadium to the plating bath.

Description: Field of the invention This invention concerns electroless copper deposition and its use in the manufacture of additive printed wiring boards. More specifically it concerns electrolessly deposited copper with improved properties of smoothness and elongation. The invention also concerns improved resistance to thermal stress and thermal cycling of copper plated-through holes. Background of the invention United States Patent No. 4,632,852 to Akahoshi et al. describes an electroless copper deposition process for additive printed wiring boards. The copper deposits obtained are described as having tensile strengths of 276 to 442 Pa and elongation on 30 µm thick test strips ranging from 3.8% to 11.1%. The electroless copper deposition solutions are operated at temperatures of 40-80°C, a sodium hydroxide concentration which will give a pH of 12.8 (measured at 25°C), and are characterized by the stabilizers comprising 1-1000 mg/l of silicon or germanium in the solution and at least 0.01 l/min per liter of injected air. United States Patent No. 4,865,888 to Akahoshi et al. describes an improvement in the process of United States Patent No. 4,632,852 wherein the air is injected in fine bubbles with a bubble diameter of 1 mm or less. The copper deposits formed by the processes of United States Patents Nos. 4,632,852 and 4,865,888 have a rough surface. Because many additive printed wiring applications require a smooth surface, the surface roughness of the copper limits its use. The roughness of the deposits is demonstrated in United States Patent No. 4,970,107 to Akahoshi et al. which describes a process wherein the electroless copper deposition bath described in United States Patent No. 4,632,852 is employed to plate over a smooth copper surface with an electroless copper deposit to a thickness of 5 µm. The surface thus produced has knife shaped projections for improving the bond when the copper surface is laminated in a multilayer printed wiring board. An additive selected from the group consisting of oxoacids of silicon, or germanium, or vanadium or carbon is employed in the electroless bath to promote formation of the knife-shaped projections. United States Patent No. 3,959,351 to Schneble et al. indicates that iron in electroless copper deposition solutions should be below 25 mg/l, preferably below 10 mg/l in order to reduce extraneous copper deposits and avoid spontaneous decomposition of the plating solution. There is no teaching in United States Patent No. 3,959,351 that trace quantities of iron affect the physical properties of the electrolessly deposited copper. The control of the iron content was important only for the stability of the electroless copper bath, not for the quality of the copper deposit. United States Patent No. 3,485,643 to Zeblisky et al. describes hexacyanoferrates as stabilizers in electroless copper deposition solutions. United States Patent No. 4,650,691 to Kinoshita et al. reports that the hexacyanoferrates decompose in the plating bath and the decomposition products inhibit further electroless copper plating and form precipitates in the bath. It indicates that the use of triethanolamine at one to three times the molar concentration of the hexacyanoferrate in the electroless bath to prevent destruction of the bath by inhibition of the plating reaction and the formation of precipitates. The triethanolamine was to prevent iron precipitation in the plating solution, and not for the quality of the copper deposit. Schneble et al., United States Patent No. 3,310,430 describes electroless copper baths containing a vanadium compound as a hydrogen inclusion retarding agent. Copper is deposited as thin foils (5-12 µm thick) with sufficient ductility to permit folding the foils in half, creasing them and unfolding the foils up to 5 times before the foil breaks at the crease. Kikuchi et al., United States Patent No. 4,563,217, discloses electroless copper baths comprising a cationic wetting agent and an inorganic compound containing silicon, germanium or vanadium to improve the stability of the plating bath and tensile strength and percent elongation of the deposited copper. While Kikuchi is silent on iron content, it should be noted that Kikuchi's solutions include conventional ingredients which as a rule contain iron. The copper deposits reported had tensile strengths of 324-657 MPa and percent elongation for 50 µm thick foils of 2-7%. If these percent elongations are normalized to copper foil 30 µm thick, the range would be 2-5%. United States Patents Nos. 3,615,732 and 3,615,735 (Shipley) disclose electroless copper plating solutions to which salts of Group VIII metals are added in concentrations such that they codeposit with copper to form an alloy having improved tensile properties. The thrust of these references is that high concentrations of Group VIII metals are codeposited (typically 22-103 mg Group VIII metal per mole of copper). Summary of the invention This invention comprises an improved process for electrolessly depositing copper from an aqueous solution containing a copper compound, a complexing agent for copper, a reducing agent for copper, a pH- adjusting agent, an additive selected from the group consisting of soluble inorganic silicon compounds and soluble inorganic germanium compounds, and in which process an oxygen containing gas is injected into the solution. The improvement comprises controlling one or more of the plating bath parameters selected from the group consisting pH, complexing agents, and sources of iron contamination such that the content of trace iron in the deposited copper layer is less than 1.5 mg per mole copper. In one embodiment, the invention comprises an improved process for electrolessly depositing copper from an aqueous solution containing a copper compound, a complexing agent for copper, a reducing agent for copper, a pH-adjusting agent, at least one additive selected from the group consisting of soluble inorganic silicon compounds and soluble inorganic germanium compounds, and in which process an oxygen containing gas is injected into the solution wherein the trace iron content is controlled by selecting the copper complexing and the operating pH such that iron present in the bath solution is held in a complex sufficient to limit the codeposited trace iron to less than 1.5 mg per mole copper. In another embodiment, the plating bath further comprises a complexing agent for iron and the operating pH is adjusted such that the formed iron complex is tight enough to limit codeposited iron in the copper layer to less than 1.5 mg per mole copper. In yet another embodiment, the invention comprises the further improvement of increasing the smoothness and ductility of the formed copper deposit by operating the plating bath with an addition agent comprising a vanadium compound. Thus, the plating bath is operated to deposit copper having a smooth surface, high ductility and a trace iron content less than 1.5 mg per mole by controlling the concentration of the pH- adjusting agent to maintain a pH of 11.2-12.0 when measured at 25°C, and increasing the smoothness and ductility of the copper deposit by operating the deposition solution with an addition agent comprising a vanadium compound. In another embodiment, the invention comprises a process for the manufacture of printed wiring boards, wherein the solution is operated to deposit copper for a printed wiring board. In particular, the solution is used to deposit the conductive pattern of a printed wiring board in a fully-additive process, or the copper deposit on the hole walls in a "partly-additive" process. The invention also pertains to an additive or partly additive printed wiring board comprising a suitable dielectric surface, such as a through hole, and a layer of copper electrolessly deposited on said surface, e.g. forming a plated through hole, wherein the layer of electrolessly deposited copper contains trace iron in a concentration below 1.5 mg per mole of copper. The present invention not only provides electroless copper deposits having improved smoothness and elongation, but also enables the manufacture of a printed wiring board displaying improved resistance to thermal stress and thermal cycling of copper plated-through holes. Thus it is possible to manufacture a printed wiring board having at least one plated through hole and capable of withstanding 25 repetitive thermal cycles without failures or an increase of more than 10% of the resistance of the plated through hole. Each thermal cycle consists of immersion in water at 25°C, followed by immersion in a fluidized sand bed at 260°C. Detailed description of the invention This invention is concerned with improvements in the products, processes and electroless copper plating baths described in United States Patents Nos. 4,632,852 and 4,865,888 which are incorporated herein by reference. It has been found that limiting the trace iron content of electrolessly deposited copper to less than 1.5 mg iron per mole of copper substantially improves the quality of the deposited copper in the ductility, percent elongation and resistance to thermal stress and thermal cycling of copper plated-through holes. Preferably, the trace iron content of the deposited copper should be less than 8 mg per mole of deposited copper. The amount of codeposited iron depends on the strength of the iron complex present in the electroless copper deposition bath. It has been found that for electroless copper baths comprising ethylenediaminetetraacetic acid (EDTA), the iron complex is not sufficiently tight at a pH exceeding 12, and that such baths should be operated at a pH not exceeding that value. When EDTA is the complexing agent, the optimum plating for minimum iron in electrolessly deposited copper is obtained when the plating bath has a pH of 11.2 to 12 (measured at 25°C). Additional complexing agents that sequester iron preferentially can be added to the plating bath as addition agents to extend the operating range. Such complexing addition agents should form a soluble complex with iron (III) at the operating temperature and pH of the plating bath. The complexing addition agent should sequester iron (III) more strongly than copper. Suitable complexing addition agents include bicine (N,N'-bis(2-hydroxyethyl)glycine) which preferentially sequesters iron (III) over copper (II) up to pH 12.5 (measured at room temperature). Complexing addition agents that strongly sequester copper (II) may be utilized in plating baths where the main complexing agent for copper forms a stronger complex with copper than the complexing addition agent, so that the complexing addition agent remains free to sequester iron (III). Surprisingly, it has been found that following such teaching substantially improves the ductility and toughness of the formed copper deposit, and crucially improves the quality of deposits on printed wiring boards with respect to the resistance to thermal stress. Additive printed wiring boards with plated- through holes in which the electroless copper deposits contain trace iron in excess of 1.5 mg per mole copper fail in thermal shock and/or thermal cycling tests. Further it has been found that the addition of small amounts of vanadium compounds to certain bath formulations following applicant's invention further improves elongation and ductility of the copper deposit as established by thermal shock and thermal cycle testing, and surprisingly eliminates the surface roughness of the copper associated with deposits formed in electroless plating baths stabilized by the addition of germanium or silicate compounds. These smooth deposits, from the use of a vanadium addition agent combined a germanium or silicate addition agent, are partcularly unexpected, in view of the teaching of Akahoshi et al., United States Patent No. 4,970,107, that vanadium addition agents produce knife-shaped projections in the copper deposit. In the electroless copper solutions described in all the aforementioned of Akahoshi et al. patents, the standard sodium hydroxide concentration is adjusted to provide a pH of 12.5-12.8 at 25°C (0.03-0.06 mole of free hydroxide). It now has been discovered that deposits from electroless copper solutions operated at lower hydroxide concentrations, to give a pH of 11.5- 12.0 at 25°C (0.003-0.010 mole of free hydroxide), preferably a pH of 11.7-11.9 at 25°C (free hydroxide concentration of 0.005-0.008 mole per liter), surprisingly had a trace iron content an order of magnitude less than that of deposits from the same copper solutions operated at the standard hydroxide concentrations of the prior art (0.03-0.06 M or a pH of 12.5-12.8 at 25°C). Correspondingly, the copper deposits from the solutions with the low hydroxide concentration had higher tensile strength and percent elongation, and additive printed wiring boards with plated-through holes plated by the electroless copper depositions solutions with lower sodium hydroxide content withstood thermal shock tests and thermal cycling better than the additive printed wiring boards with plated-through holes plated in the conventional solutions described by Akahoshi et al. Applicant has discovered that a further improvement in the properties of the copper deposit is obtained by the addition to the electroless copper deposition bath of trace amounts of a vanadium compound. The addition of such trace amounts of a vanadium compound further increases the deposit elongation and toughness as measured by thermal shock and thermal cycle resistance of the deposits. Surprisingly, applicant also has found that the surface roughness associated with the deposits from an electroless copper bath stabilized by a germanium or silicate stabilizer and a polyethylene glycol are eliminated by the addition of a small but effective amount of a vanadium compound. The copper concentration in the electroless deposition bath is 0.02-0.08 mol/l, preferably 0.3-0.6 and most preferably 0.036-0.048 mol/l. The copper concentration in the deposition bath is replenished to maintain the copper concentration as copper is deposited from the bath. If the copper compound in the replenishment solution contains more than 1 mg of iron per mole of copper, an iron complexing addition agent may be needed. Preferably the copper replenishment solution will contain less than 1 mg of iron per mole of copper and more preferably less than 0.5 mg of iron per mole of copper. When an iron complexing agent is required, the concentration of the iron complexing agent should be 1-10 millimoles per millimole of iron, and when bicine is the iron complexing agent preferably 0.05-1 mg/l in the copper deposition bath. The concentration of the copper complexing agent should be 0.04-0.08 mol/l greater than the concentration of copper, and preferably 0.05-0.06 mol/l greater than the copper concentration. When the complexing agent is too low, the bath deposits copper outside of the conductor pattern; when it is too high, the plating rate slows down. The formaldehyde concentration is 0.04-0.9 mol/l; preferably, 0.045-0.067 mol/l, and more preferably 0.053-0.060 mol/l. The formaldehyde replenishment solution should contain less than 0.2 mg of iron per mole formaldehyde, preferably less than 0.1 mg per mole formaldehyde. The hydroxide replenishment solution should contain less than 0.3 mg of iron per mole hydroxide preferable less than 0.15 mg of iron per mole hydroxide. The electroless copper bath may contain as stabilizers from 10-1000 mg/l of a soluble inorganic silicon compound in terms of silicon atom or 10-1000 mg/l of an inorganic germanium compound in terms of germanium atom in conjunction with a polyoxyethylene compound. Preferably the electroless copper bath will contain as stabilizers from 25-100 mg/l of germanium or in conjunction with a polyoxyethylene compound. Baths with less than 25 mg/l germanium are significantly less stable. Baths operated with germanium concentrations up to 250 mg/l may produce deposits with a slight improvement in percent elongation, but the plating rate decreases when the germanium concentration is above 100 mg/l. The concentration of compounds containing polyoxyethylene in the plating solution should be equivalent to 5-50 ethylene oxide units per liter. Preferably, the polyoxyethylene compound is selected from the group of ethylene glycol polymers with a molecular weight between 250 and 250,000 daltons. More preferably, the polymer has a molecular weight between 600 and 2000 daltons, and most preferably between 800 and 1400 daltons. Ethylene glycol polymers are used at a concentration of 0.1-10 g/l; preferably, 0.5-4 g/l, and more preferably, 1-2 g/l. The concentration of vanadium in the plating bath should be 0.5-2.5 mg/l. There is no significant increase in the smoothness or percent elongation of the copper deposited from solutions containing less than 0.5 mg/l vanadium. Deposits from solutions containing greater than 2.5 mg/l vanadium exhibit a percent elongation comparable to deposits from solutions containing lower vanadium concentrations, but the deposition rate is approximately 60% slower. Fine air bubbles should be introduced into the electroless copper deposition bath at a rate of 0.04-3 liters of air per minute per liter of bath; preferably, 0.06-0.1 liters of air per minute per liter of bath. Other details of the invention are given in the claims. The present invention will be further illustrated in the examples below. In the examples, the copper deposits varied in thickness. A standard tensile strength calculation includes a correction for the thickness of the deposit, but the standard percent elongation does not. In the following examples, to compare the percent elongation of deposits with varying thicknesses, the thicknesses were normalized to 30 µm. Example 1 An electroless copper bath was operated with the following formulation: Large air bubbles came from a pipe with 0.6 mm diameter holes. Fine air bubbles came from a porous walled pipe. The plating bath was operated with a load of 1.5 dm 2 of surface being plated per liter. Copper also was deposited on a stainless steel substratum to obtain a foil suitable for tensile testing. The rate of copper deposition was 6-7 µm/hr. The next day the pH of the electroless copper bath was changed and the bath was operated at the following formulation: The plating bath was operated with a load of 1.5 dm 2 of surface being plated per liter. Copper also was deposited on a stainless steel substratum to obtain a foil suitable for tensile testing. The rate of copper deposition was 6-7 µm/hr. The plating bath was operated for two more days at pH 11.8 at 25°C. After each day the copper deposited on the stainless steel substratum was dried for 1 hour at 160°C. After drying a copper foil 50 pm thick was removed from the stainless steel. A portion of the foil was used for tensile testing, and a portion was analyzed for the trace iron content. The results are reported in the Table 1. The percent elongation is reported as measured at the deposit thickness and as normalized to a thickness of 30 µm. Bath pH Iron Conc. in the Copper Tensile Strength Deposit Thickness % Elongation 25°C mg/mol MPa µm As measured Normalized 30 µm 12.5 3.50 331 49.5 2 2 11.8 0.53 413 27.2 6 7 11.8 0.54 400 29.2 8 8 11.8 0.53 455 30.5 9 9 Example 2 The copper deposits produced in the plating formulations of Example 1 had a rough surface. The surface roughness was 1.5-2.0 µm. The formulations described in Example 1 were modified by the addition of a vanadium compound to improve the surface finish and the ductility of the deposit. An electroless copper bath was operated with the following formulation: CuSO4 5H2O g/l 10 Na4EDTA 2H2O g/l 41 NaOH pH at 25°C 11.8 Formaldehyde (37% solution) ml/l 4.3 By-product Na2SO4 mol/l 0.25 By-product NaOOCH mol/l 0.5 Polyoxyethylene (MW=1000) g/l 1 GeO2 mg/l 70 V2O5 mg/l 2 Air injection (large bubbles) l/min/l(bath) 0.07 Air injection (fine bubbles) l/min/l(bath) 0.07 Temperature °C 72 The plating bath was operated with a load of 1.5 dm 2 of surface being plated per liter. The rate of copper deposition was 4.5-5.5 µm/hr. The surface finish of the copper deposit was 0.5-1.0 µm. The 26 µm copper foil deposited on the stainless steel substratum was dried for 1 hour at 160°C. A tensile test was performed on the foil. The tensile strength was 345 MPa and the elongation was 18% (20% when normalized to 30 µm thick deposit). The plating bath also was operated with a work loads of 1.2 and 2.5 dm 2 per liter, and equivalent results were obtained. Example 3 Plating baths having the same formulation as Example 2 were operated on five different days to provide samples for tensile testing. After each day, the copper deposited on the stainless steel substratum was dried for 4 hours at 160°C. The results are reported in the Table 2. The percent elongation is reported as measured at the deposit thickness and as normalized to a thickness of 30 µm. Plating Run Deposit Thickness Tensile Strength % Elongation µm MPa As measured Normalized 30 µm 1 26.1±0.3 326±4 18±2 20 2 36.8±0.3 314±3 21±2 18 3 24.1±0.5 323±6 14±1 17 4 16.8±0.3 318±3 12±2 17 5 24.1±0.3 306±3 18±1 21 Example 4 Printed wiring boards were prepared by the partly additive process. In the partly additive process a 1.6 mm thick, base material, copperclad on both sides, was drilled to provide through holes with 0.33 mm diameter; the hole walls were activated and electrolessly plated with 1-2 µm of copper; a double- sided "daisy-chain" pattern was applied with a tenting resist which covered the through holes; the conductive pattern was formed by etching, and the resist was stripped. A permanent resist was applied on both sides over the conductive pattern leaving the through holes and the lands exposed. The lands and the walls of the through holes were electrolessly plated with copper using an electroless copper deposition bath operated with the low pH formulation of Example 1. After plating, the printed wiring boards were dried for 4 hours at 160°C. The plated-through holes in the printed wiring boards were subjected to the fluid sand thermal cycling test described in IPC TECHNICAL REPORT, IPC-TR- 579, ROUND ROBIN RELIABILITY EVALUATION OF SMALL DIAMETER PLATED THROUGH HOLES IN PRINTED WIRING BOARDS. Lincolnwood, IL: Institute for Interconnecting and Packaging Electronic Circuits, 1988, p25. In one cycle of the test, printed wiring boards are immersed in water at 25°C, withdrawn and the excess water removed, and immersed in a fluidized sand bath at 260°C. The boards are cycled to failure, which is an open circuit or a 10% increase in the resistance of the chain of plated-through holes. Thirty cycles without failure is considered equivalent to passing 400 cycles of MIL-STD- 202 thermal cycle test. Table 3 shows the thickness and tensile properties of the copper deposit with the results of the fluid sand thermal cycling test. Plating Run Deposit Thickness Tensile Strength % Elongation Cycle To Failure µm MPa As measured Normalized 30 µm 1 51 273±2 12±1 7 40 2 53 241±4 12±2 7 34 3 48 262±3 13±1 8 42 Example 5 Example 4 was repeated except that the hole walls were plated with an electroless copper deposition bath operating with the formulation of Example 2. A sample of the copper foil was analyzed and the iron content was found to be 0.34 mg per mole copper. Table 4 below shows the thickness and tensile properties of the copper deposit and the results of the fluid sand thermal cycling test. Plating Run Deposit Thickness Tensile Strength % Elongation Cycle To Failure µm MPa As measured Normalized 30 µm 1 48 ----- ---- -- 44 2 23 290±5 10±1 13 63 3 30 315±3 17±4 17 44 These excellent results especially for thin foils further illustrate the surprising toughness and ductility of the electroless copper deposits when a small effective amount of a vanadium compound is dissolved in the electoless copper deposition bath. Comparative Example Example 5 was repeated except that the electroless copper deposition solution had a trace iron content of 2.2 mg iron per mole of copper from replenishment with copper sulfate solution contaminated with 32 mg iron per mole of copper sulfate. The results of tensile testing of the copper deposited are shown in Table 5. Plating Run Deposit Thickness Tensile Strength % Elongation Iron in Copper Foil µm MPa As measured Normalized 30 µm ppm 1 23 455±7 6±1 7 205 2 29 434±1 6±1 6 62 This demonstrates that when the trace iron in the plating solution is high, even operating the electroless copper deposition solution at a pH between 11.3 and 12.0 is not sufficient to maintain low iron in the deposit and the deposits obtained will have lower ductility. Example 6 Example 5 is repeated using the copper sulfate replenishment solution containing 32 mg iron per mole copper sulfate, but the electroless copper plating bath is modified by an iron complexing addition agent. The complexing addition agent is bicene. Five grams of bicene is added to each liter of the copper sulfate replenishment solution. Copper is electrolessly plated from the bath; the copper has high thermal shock resistance and less than 1.5 mg iron per mole of copper.

Claims: A process for the formation of an electroless copper deposit from a plating bath comprising an aqueous solution containing a copper compound, a complexing agent for copper, a reducing agent for copper, a pH-adjusting agent, an additive selected from the group consisting of soluble inorganic silicon compounds and soluble inorganic germanium compounds, and in which process an oxygen containing gas is injected into the solution, characterized in that one or more of the plating bath parameters pH, complexing agents, sources of iron, or combinations of these parameters, are controlled so as to limit the content of trace iron in the deposited copper layer to a value below 1.5 mg per mole of copper. A process according to claim 1, characterized in that the trace iron content is controlled by selecting the copper complexing and the operating pH such that iron present in the bath solution is held in a complex sufficient to limit the codeposited trace iron to less than 1.5 mg per mole copper. A process according to claim 2, characterized in that the complexing agent is EDTA and the pH is controlled and maintained at a value in the range of from 11.2 to 12 when measured at 25°C. A process according to claim 3, characterized in that the solution contains 0.036-0.048 mol/l copper compound, 0.086-0.106 mol/l EDTA, 0.053-0.060 mol/l formaldehyde, 0.1-10 g/l polyoxyethylene compound, and 25-100 mg/l germanium. A process according to any one of the preceding claims, characterized in that the plating bath is operated with an addition comprising a vanadium compound. A process according to claim 5, characterized in that the vanadium compound is present in the plating bath in a concentration of 0.5-2.5 mg/l. A process according to any one of the preceding claims, characterized in that the copper compound in the plating bath is replenished by a copper compound containing less than 10 mg of iron per mole of copper. A process according to claim 7, characterized in that the replenishing copper compound contains less than 5 mg of iron per mole of copper. A method of manufacturing a printed wiring board wherein an electroless copper deposit is formed on a suitable dielectric substrate, characterized in that the copper deposit is formed by a process according to any one of the preceding claims. An additive or partly additive printed wiring board comprising a suitable dielectric surface, and a layer of copper electrolessly deposited on said surface, characterized in that the layer of deposited copper contains trace iron in a concentration below 1.5 mg per mole of copper.

Inventors: MAYERNIK RICHARD ARTHUR, MAYERNIK, RICHARD ARTHUR
Applicants: AMP AKZO CORP, AMP+AKZO
Application year: 1993
Main classification: C23C18
IPC codes: C23C18, H05K3