Electroless Cobalt Deposition from Acid Baths

F. Pearlstein and R. F. Weightman

Pitman-Dunn Laboratory, Frankford Arsenal, Philadelphia, Pennsylvania 19137
The publication costs of this article have been assisted by the Department o] the Army.

ABSTRACT A n acid electroless cobalt p l a t i n g b a t h was d e v e l o p e d w h i c h utilizes d i m e t h y l a m i n e b o r a n e (DMAB) as the reducing agent and w h i c h provides b r i g h t deposits at o v e r 13 ~ m / h r at 70~ The bath, s l i g h t l y modified, is also usable at room t e m p e r a t u r e for deposition on p a l l a d i u m - a c t i v a t e d nonconductors. A d d i t i o n s of even small quantities of h y p o p h o s p h i t e to the DMAB b a t h r e s u l t e d in failure to achieve deposition; the effect of h y p o p h o s p h i t e additions on the single electrode potentials was d e t e r m i n e d and the results discussed. Eleetroless c o b a l t - b o r o n deposits w~re found superior, in some r e spects, to electroless n i c k e l - p h o s p h o r u s for p r o v i d i n g protection for steel against corrosive attack. A double l a y e r deposit of electroless nickel plus electroless cobalt topcoat p r o v i d e d m o r e effective p r o t e c t i o n for steel t h a n either deposit, alone, of the same total thickness. C h r o m a t i n g t r e a t m e n t s w e r e f o u n d effective for r e t a r d i n g the t e n d e n c y for t a r n i s h i n g of cobalt d u r i n g salt exposure. The m a g n e t i c p r o p e r t i e s of some electroless c o b a l t - b o r o n d e posits w e r e d e t e r m i n e d ; the coercivity was c o n s i d e r a b l y l o w e r t h a n t h a t of electroless c o b a l t - p h o s p h o r u s deposits.

Electroless cobalt deposition was first described b y B r e n n e r and Riddell (1). Since t h a t time, a g r e a t deal of interest has been shown in the electroless cobalt deposits because of t h e i r a b i l i t y to be r e a d i l y p l a t e d upon s u i t a b l y a c t i v a t e d plastic (2) and because o f the wide v a r i e t y of m a g n e t i c p r o p e r t i e s attainable. Electroless cobalt deposits h a v e been e m p l o y e d for high quality, high d e n s i t y recordings and for c o m p u t e r storage elements in high speed switching devices (3). The m a g n e t i c deposits are p r o d u c e d from h y p o p h o s p h i t e - b a s e d baths and consist of c o b a l t - p h o s p h o r u s (4-10) or t e r n a r y alloys of cobalt and phosphorus plus an additional m e t a l e l e m e n t (11-18). It is well k n o w n t h a t from baths containing h y p o phosphite reducing agent, electroless cobalt deposits can be p r o d u c e d only from a l k a l i n e - t y p e baths w h e r e as nickel deposits are p r o d u c e d from both a l k a l i n e and acid baths (19). The a c i d : t y p e electroless nickel b a t h s h a v e e n j o y e d the g r e a t e r commercial acceptance b e cause of h i g h e r deposition rates and e l i m i n a t i o n of u n pleasant a m m o n i a fumes. In the desire to develop a useful a c i d - t y p e electroless cobalt p l a t i n g bath, a t t e n tion was d i r e c t e d to the use of other reducing agents. D i m e t h y l a m i n e b o r a n e (DMAB), for example, is a m o r e p o w e r f u l reducing agent t h a n h y p o p h o s p h i t e and is capable of p r o v i d i n g electroless cobalt deposits from both acid and a l k a l i n e b a t h s (20, 21). The studies r e p o r t e d h e r e i n w e r e conducted to d e velop acid electroless cobalt plating baths and to d e t e r m i n e some characteristics of the baths a n d p r o p e r ties of deposits.

Experimental
P r e l i m i n a r y studies i n v o l v e d p r e p a r a t i o n of acidt y p e electroless cobalt p l a t i n g baths containing cobalt sulfate, d i m e t h y l a m i n e b o r a n e ( D M A B ) , and an o r ganic radical (to function as buffer, exaltant, a n d / o r chelate) such as acetate, lactate, citrate, succinate, o r glycolate. Succinate was indicated from these e x p e r i ments to be the most effective additive of the group for p r o v i d i n g sound deposits at high rates. E x p e r i m e n t a l electroless cobalt plating baths w e r e p r e p a r e d w i t h r e a g e n t g r a d e chemicals except for DMAB 1 which was 99~-% purity. A t h e r m o s t a t i c a l l y controlled w a t e r b a t h was used to h e a t and m a i n t a i n solutions w i t h i n 1.0~ of the desired t e m p e r a t u r e .
Key words: electroless plating, cobalt, nickel, amine borane, hypophosphlte. i Callery C h e m i c a l C o m p a n y , Callery, P e n n s y l v a n i a 16024.

Copper panels (2 2.5 cm) w e r e a l k a l i n e cleaned, chemically polished, a n d p a l l a d i u m a c t i v a t e d [30 sec in a solution of 0.1 g / l i t e r PdCI~ and 0.1 m l / l i t e r HC1 (38%) a t 25~ t h o r o u g h l y rinsed, dried, a n d r e weighed. Deposition tests w e r e conducted for a 1 h r p e r i o d w i t h an a r e a to volume ratio of 1: 20. The effect of b a t h constituent concentration, b a t h pH, and b a t h t e m p e r a t u r e on electroless cobalt deposition r a t e was determined. The effect of h y p o p h o s p h i t e additions to a n acidt y p e electroless cobalt plating b a t h (utilizing DMAB reducing agent) on deposition r a t e was determined. The s t e a d y - s t a t e potential of 13 gm electroless cobaltboron p l a t e d specimen in the baths of m i x e d D M A B h y p o p h o s p h i t e was also d e t e r m i n e d . The specimen was successively i m m e r s e d for 5 rain periods into baths (at 70~ containing 0, 0.25, 0.5, 1.0, 2.0, 4.0, 6.0, and 82 g a i t e r sodium h y p o p h o s p h i t e m o n o h y d r a t e . The potential of the specimen was m e a s u r e d at t h e end of each 5 rain i m m e r s i o n p e r i o d vs. a s a t u r a t e d calomel electrode i m m e r s e d into the b a t h for 5 sec. A H e w l e t t P a c k a r d 410C Vacuum Tube Voltmeter, w i t h i n p u t resistance of l0 s ohms was used for t a k i n g the p o t e n tial measurements. S i m i l a r tests w e r e conducted with an a l k a l i n e cobalt b a t h 2 containing various p r o p o r tions of DMAB and h y p o p h o s p h i t e and with the acid and alkaline b a t h in which the cobalt salt was r e placed w i t h the m o l a r e q u i v a l e n t of nickel sulfate. The a b i l i t y for clean, n o n a c t i v a t e d copper to spont a n e o u s l y initiate d e p o s i t i o n of cobalt from t h e acidt y p e electroless plating b a t h at 70~ was d e t e r m i n e d as a function of DMAB concentration. P o t e n t i a l m e a surements were also made. Deposition tests w e r e conducted on other substrates including steel, electroless nickel, platinum, and p a l l a d i u m - a c t i v a t e d plastic. A h e a v y (about 200 ~m) deposit of electroless cob a l t was a p p l i e d to steel and h a r d n e s s m e a s u r e m e n t s m a d e p e r p e n d i c u l a r to the surface using a Vickers i n d e n t o r w i t h 50g load applied. The deposit h a r d n e s s was also d e t e r m i n e d a f t e r h e a t - t r e a t m e n t at 250~ in an air oven. Electroless cobalt deposits w e r e a n a l y z e d for composition, i.e., cobalt (electrodeposition m e t h o d ) , boron (atomic absorption m e t h o d ) , carbon (Leco A u t o m a t i c Carbon D e t e r m i n a t o r ) , and n i t r o g e n ( K j e l d a h l distillation-titration method).
~35 g / l i t e r COSO4 .YHsO, 80 g / l i t e r Na~C~-I~O7.2H20, SO g / l i t e r NH4C1, 60 m l / l i t e r N I ~ O H (28% NHs); 80~

1023
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1024

J. Eleetrochem. Soe.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y

A u g u s t 1974

Electroless cobalt deposits were applied to steel Hull Cell panels 3 (6.7 X 10 cm) from the acid-DMAB bath i n n o m i n a l thicknesses of 2.5, 5, and 10 ~ n a n d tested for corrosion resistance d u r i n g exposure to 5% n e u t r a l salt spray. For comparative purposes, tests were also conducted with conventional electroless n i c k e l - p h o s phorus 4 plated steel panels. A set of panels was also prepared with a double layer deposit consisting of approximately 7.5 ~m electroless nickel followed b y a topcoat of 2.5 ~m electroless cobalt and subjected to the salt spray test. Triplicate panels were p r e p a r e d for each type and thickness of deposit was tested. The steel panels were prepared for electroless plating as follows: (i) 1 m i n in 50% (volume) hydrochloric acid (38%) at 25~ (to remove protective zinc coating), cold w a t e r rinse (CWR); (ii) 5 m i n i n orthosilicate soak alkaline cleaning b a t h at 85~ a n d soft bristle brushing, CWR; (iii) 1 m i n i n 50% (volume) hydrochloric acid (38%) at 25~ CWR. Chromating t r e a t m e n t s were applied to electroless cobalt, freshly deposited on steel, b y i m m e r s i o n for 10 see i n 200 g / l i t e r Na2Cr20~-2H20 --6 m l A i t e r H~SO4 (sp. gr. 1.84) or i n Alodine 1200S 5 (7.5 g/liter, pH 2.1) at 25~ rinsed, and dried. The specimens were e v a l u ated for t a r n i s h resistance d u r i n g salt spray exposure. Cobalt deposits were applied to chemically polished and p a l l a d i u m - a c t i v a t e d copper panels from the following baths:
Bath constituent
C o b a l t s u l f a t e , CoSO4 9~ (g/liter)

BATH INSTABILITY

16.0

~: ~12.0 S o ~, E a; ~ 8.0 " (.9 z ~ 4.0

I
0 2

I
4

I
6

I
8

Co-B Co-B (acid) (alk)

25 4 -30 4 -8050 60 80 9.0

Co-P (alk) 30 -20 80 50 60 80 9.0

DMAB CONCENTRATION g / ~ Fig. |. Effect of DMAB concentration on electroless cobalt plating rate. Bath: 25 g/llter COS04- 7H~O, ~5 g/liter C4H4Na204 " 6H~O; pH 5.0; temp. 80~

D M A B , (CHz) 2Hi~BI'][a
S o d i u m h y p o p h o s p h t t e , NaH2PO~ 9 H 2 0 ( g / l i t e r ) Sodium s u c c i n a t e , CdW4Na~O~ 9 6 ~ (g/liter) S o d i u m c i t r a t e , NaaCeH~O~ 92I-I~O ( g / l i t e r ) A m m o n i u m c h l o r i d e , NI-]hC1 ( g / l i t e r ) A m m o n i u m h y d r o x i d e (28% NI-I~), NI-I~OH ( m l / liter) Temperature, ~

25

---

pH

~ 70 5,0

The coercive force of various thicknesses of the deposits was d e t e r m i n e d using a v i b r a t i n g sample m a g netometer.8 Results and Discussion The effect of d i m e t h y l a m i n e b o r a n e (DMAB) concentration on deposition rate was d e t e r m i n e d from solutions c o n t a i n i n g 25 g a i t e r cobalt sulfate h e p t a h y drate and 15 g a i t e r sodium succinate hexahydrate. Results are shown in Fig. 1. The baths were adjusted to pH 5.0 with sulfuric acid solution and were operated at 80~ Deposition rates increased essentially l i n e a r l y with DMAB concentration to a m a x i m u m at about 4 g a i t e r . At above this DMAB concentration, catalytic particles formed i n the solution which tended to settle to the b e a k e r bottom a n d resulted i n rapid bath decomposition. The effect of succinate concentration on deposition rate was d e t e r m i n e d from solutions containing 25 g a i t e r cobalt sulfate h e p t a h y d r a t e and 4 g a i t e r DMAB at pH 5.0 a n d at 80~ (see Fig. 2). W h e n no succinate was present, spongy cobalt formed w i t h i n the solution accompanied b y rapid bath decomposition, a n d virt u a l l y no deposition was produced o n the p a l l a d i u m activated copper specimen. Satisfactory bath stability was provided b y the presence of 10 g a i t e r or more of the succinate in the bath. Succinate also provided buffering action, i.e., p r e v e n t e d rapid change i n bath pH d u r i n g deposition. Deposition rates were highest and essentially constant at sodium succinate h e x a h y d r a t e concentration of 15-30 g a i t e r . A 25 g a i t e r concentration was adopted for additional studies. The effect of bath pH (measured at 25~ on deposition rates was determined. Both initial pH and the pH after completion of deposition test are shown i n Fig. 3.
O. H u l l C o m p a n y , I n c o r p o r a t e d , C l e v e l a n d , O h i o 44102. 4 B a t h : 25 g / l i t e r N i S O ~ . 6H~O, 9 g / l i t e r NaCsHaO2, 22.5 g / l i t e r NaH:~/:'Os 9 H~O, 0.001 g / l i t e r P b (C.,_I~O-.~)~ - 3H-zO; p H 4.6; 85~ A m c h e m P r o d u c t s , I n c o r p o r a t e d , A m b l e r . P e n n s y l v a n i a 19002. e Princeton Applied Research Corporation, Princeton, New Jersey

la.o INSTABRITY~

"0"~0

E IZ,O
?,
E

~a.o

~- 4o

SODIUMSUCCINATE (aH20}CONCENTRAT~ON g/,~

Fig. 2. Effect of succinate concentration on electroless cobalt plating rate. Bath: 25 g/liter COSO4-7H20, 4 g/liter DMAB; pH 5.0; temp. 80~

The deposition rate increased m a r k e d l y w i t h b a t h pH. Baths of pH above about 5.5 t e n d e d to be u n s t a b l e and deposits formed on beaker walls and bottom. It is interesting to note that baths at pH 4.5 or lower increased in pH d u r i n g the deposition test, while baths at pH 5.5 or above decreased. Normally, electroless plating baths decrease i n pH d u r i n g use because h y drogen ions are a product of the reaction (19, 22). However, DMAB is subject to acid catalyzed hydrolysis (24) leading to consumption of H + (CI-Iz)2HN 9 B H s -5 3 H ~ O -5 H +
-~ (CI%)2NI-I~ + -5 H, B O 3 -5 3H2 Indeed, it was found that even w h e n no electroless plating was occurring, baths (80~ at p H 4.5 or below increased in p H with time, and that gassing was evident within the solutions. At bath p H of 5.0, little

s R.

08540.

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VoL 121, No. 8

ELECTROLESS COBALT DEPOSITION

of p r i m a r y importance. A t 70~

1025

~O,C

//

1 s"I

le,o

IZ.O

u~

s.o

-- -- -- BATH INSTABILITY

3.s

4.0

4~s
BATH pit

5'.o

~s

e~

Fig. 3. Effect of bath pH on electroless cobalt plating rate. Bath: 25 g/liter COSO4.7H:20, 25 g/liter C4H4Na204" 6H20, 4 g/liter DMAB; temp. 80~

change in p H r e s u l t e d d u r i n g (or w i t h o u t ) deposition and subsequent tests w e r e conducted w i t h baths at this p H unless otherwise noted. Electroless cobalt deposition r a t e s w e r e little affected b y cobalt salt concentration w i t h i n the r a n g e of 15-45 g / l i t e r a n d tests w e r e continued w i t h b a t h s containing 25 g a i t e r cobalt sulfate h e p t a h y d r a t e . The r a t e of cobalt deposition increased w i t h increasing b a t h t e m p e r a t u r e in a m a n n e r t y p i c a l of most electroless p l a t i n g b a t h s (24-26) (see Fig. 4). A t 90~ the b a t h was subject to spontaneous production of cobalt particles and r a p i d decomposition. A t 80~ the b a t h was stable d u r i n g the 1 h r plating tests b u t t h e r e w a s a t e n d e n c y for c a t a l y t i c p a r t i c l e s to f o r m in t h e b a t h d u r i n g m o r e e x t e n d e d plating periods t h e r e b y causing b a t h decomposition. The b a t h can be m a d e m u c h less susceptible to such decomposition b y i n t r o ducing trace amounts of a catalytic poison (e.g., 1-2 r a g / l i t e r lead acetate t r i h y d r a t e or t h i o u r e a ) . H o w ever, at b a t h t e m p e r a t u r e s of 80~ o r above, w a s t e f u l consumption of DMAB b y h y d r o l y s i s is p r o b a b l y significant (23) and it is thus advisable, from a p r a c tical standpoint, to o p e r a t e the b a t h at l o w e r t e m p e r a t u r e s except w h e r e v e r y high deposition rates a r e

the b a t h is o p e r a b l e w i t h o u t the necessity of a d d i t i o n of catalytic poison stabilizers, and h y d r o l y s i s losses are minimized. Deposition rates a r e quite low at a b a t h t e m p e r a t u r e of 40~ or lower. However, the b a t h s can b e u s e d even at room t e m p e r a t u r e s (22~176 for a p p l y i n g thin, conductive deposits to p a l l a d i u m - a c t i v a t e d nonconductors, p r o v i d e d the b a t h p H is i n c r e a s e d to a b o u t 6.3. T h e r e was a t e n d e n c y f o r gas pits to form on t h e electr01ess cobalt deposits. W o r k p i e c e m o v e m e n t was helpful in a l l e v i a t i n g this condition, b u t a d d i t i o n to the b a t h of about 15 g / l i t e r or m o r e sodium sulfate also r e d u c e d t h e t e n d e n c y for pitting to occur. The presence of sodium sulfate in the b a t h h a d no a p p a r e n t deleterious effects and did not affect deposition rate. The electroless plating b a t h of p r e f e r r e d composition is 25 g a i t e r cobalt sulfate ( C O S O 4 . 7 H 2 0 ) , 25 g a i t e r sodium succinate (C4H4Na204-6H~O), 15 g / l i t e r sod i u m sulfate (Na~SO4), and 4 g / l i t e r d i m e t h y l a m i n e b o r a n e [ (CH3)~HNBH~]. The b a t h at p,H 5.0 a n d at a t e m p e r a t u r e of 70~ produces b r i g h t electroless cobalt deposits at a r a t e of about 13 ~m/hr. Baths of mimed DMAB-hypophosphite.--The effect of h y p o p h o s p h i t e additions to the electroless cobalt plating b a t h on deposition r a t e at 70~ is shown in Fig. 5. As little as 1 g a i t e r sodium h y p o p h o s p h i t e m o n o h y d r a t e s u b s t a n t i a l l y r e d u c e d t h e deposition rate; 4 g / l i t e r or m o r e p r e v e n t e d deposition entirely. I t was thus d e m o n s t r a t e d that, not only is h y p o p h o s p h i t e r e ducing agent u n a b l e to p r o v i d e electroless cobalt d e p osition from acid solutions, b u t its presence p r e v e n t s deposition from a DMAB bath. The s t e a d y - s t a t e m i x e d potentials of an electroless cobalt specimen in the baths of increasing h y p o p h o s p h i t e concentrations a r e also shown in Fig. 5. The curve of potentials vs. h y p o phosphite concentration closely p a r a l l e l e d t h a t of d e p osition rate. The deposition potential for cobalt in t h e electroless plating b a t h (70~ p H 5.0), b u t from w h i c h the r e ducing agents w e r e excluded, was d e t e r m i n e d b y a p p l y i n g increasing cathodic c u r r e n t in v e r y small i n c r e m e n t s to a gold electrode. T h e cathode p o t e n t i a l at which the f i r s t signs of cobalt deposition a p p e a r e d was about --0.67V (SCE).~
7 S i m i l a r t e s t s w e r e c o n d u c t e d i n t h e s a m e b a t h b u t w i t h 23.4 g / l i t e r NiSO4 9 6H~O p r e s e n t i n s t e a d o f t h e c o b a l t salt, T h e d e p o s i tion p o t e n t i a l f o r n i c k e l w a s d e t e r m i n e d t o b e about - - 0 , 5 9 V ( S a E ) .

I0.( : ~
l

- 0.76

BATH 16.0
INSTABILITY

S.O ~ (M E 6.(:

-O.T2

- 0.68 O

EI2.0 s
~ 8.0

b;
"" 4.0

POTENTIAL
2.0

I-

4X

~PLATIN

~
~0 40 so I eo ! 70 I 80

--~

RATE

"O.BO

SOD, HYPOPHOSPHITE (HzO) CONC.~ g/L

BATH TEMPERATURE,~

Fig. 4. Effect of bath temperature on electrnless cobalt plating rate. Bath: 25 g/liter COSO4 7H20, 25 g/liter C4H4Na204 9 6H20, 4 g/liter DMAB; pH 5.0.
9

Fig. 5. Effect of hypophosphite additions to bath on electroless cobalt plating rate and potential. Bath: 25 g/liter COSO4- 7H20, 25 g/liter C4H4Na~O4 9 6H~O, 15 g/liter No2504, 4 g/liter DMAB; pH 5.0; temp, 70~

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1026

J. Electrochem. Soc.: E L E C T R O C H E M I C A L

SCIENCE

AND

TECHNOLOGY

A u g u s t 1974

It can be seen from Fig. 5 t h a t w h e n about 2 g a i t e r or m o r e of t h e h y p o p h o s p h i t e is p r e s e n t in t h e bath, t h e s t e a d y - s t a t e m i x e d p o t e n t i a l of t h e catalytic s u r face is not a t t a i n e d at which cobalt can be deposited and is at a level characteristic for baths containing h y p o p h o s p h i t e alone. Gassing at the p a l l a d i u m - a c t i v a t e d specimens was o b s e r v e d in all solutions, t h o u g h the r a t e was c o n s i d e r a b l y decreased in the baths from which deposition was not obtained. The action of h y pophosphite m a y be considered analogous to l o w e r i n g the h y d r o g e n o v e r v o l t a g e of a surface and thus p r e venting t h e m e t a l deposition from occurring. The effect of h y p o p h o s p h i t e - D M A B combinations in a l k a l i n e electroless cobalt plating baths, from which deposits a r e p r o d u c e d w h e n e i t h e r reducing agent is present alone, on deposition r a t e a n d p o t e n t i a l are shown in Fig. 6. M a r k e d antagonism is indicated b e t w e e n t h e h y p o p h o s p h i t e a n d DMAB from t h e d e p osition r a t e m e a s u r e m e n t s , a n d solutions w i t h r e l a t i v e l y little h y p o p h o s p h i t e b e h a v e m o r e like b a t h s containing o n l y hypophosphite. The h y p o p h o s p h i t e m i g h t be considered as p r e f e r e n t i a l l y adsorbing or d e h y d r o g e n a t i n g on the surface t h e r e b y n u l l i f y i n g the presence of DMAB. The decrease in s t e a d y - s t a t e m i x e d potential of electroless cobalt is most p r o nounced in the solutions containing little h y p o p h o s p h i t e and it decreases m o r e g r a d u a l l y w i t h f u r t h e r increases in hypophosphite. S i m i l a r studies of nickel deposition r a t e in m i x e d h y p o p h o s p h i t e - D M A B b a t h s w e r e conducted from both acid a n d a l k a l i n e solutions. M a r k e d antagonism was not e x h i b i t e d for the nickel plating b a t h s (see Fig. 7). Nickel deposition rates from the a l k a l i n e b a t h s w e r e not g r e a t l y affected b y the r e l a t i v e p r o p o r t i o n s of h y pophosphite a n d DMAB (see Fig. 8). It is e v i d e n t t h a t t h e m e t a l ions also p r o v i d e some i n t e r a c t i o n w i t h one or b o t h of the reducing agents as w i t n e s s e d b y the differences in b e h a v i o r of the cobalt a n d nickel baths.

ol ,
b: ,c

m.c

-I
S.O
. . . . . . . . . . . ~p._C~CEy_T_~_T_~_N.g.C~_ . . . . . . . . . 0 4 8 19' 16. SOD. HYPOPHOSPHITE(H20) CONCENTRATION,glJb I0.0

Fig. 7. Effect of DMAB-hypophosphite combinotions on electroless nickel ploting rote. Both: 23.4 g/liter NiSO4.6H20, 25 g/ liter C~H4N~O4" 6H20, ]5 g/liter No2SO4; pH 5.0; temp. 70~

S,O

Deposition on various substrates.--Substrates t h a t are sufficiently c a t a l y t i c a l l y active to spontaneously initiate deposition b y i m m e r s i o n in the (25-25-15-4) electroless cobalt plating b a t h (pH 5.0, 70~ a r e steel, electroless nickel, palladium, o r gold. A l u m i n u m is s p o n t a n e o u s l y plated, p r e s u m a b l y b y first p r o v i d i n g a displacement deposit of cobalt. A thin i m m e r s i o n zinc

~4c
L9

Z.O

t
S.
J=

04

I 3

I 2 I DMAB~NC'ENTRATION. g / J

! 0

I0 15 20 SOO.HYPOPHOSPHITE (H,40) CONCENTRATION~g/,~

Fig. 8. Effect of DMAB-hypophosphlte combinations on electroless nickel plating rate from alkaline bath. Bath: 32 g/liter NiSO4- 6H~O, 80 g/liter Ha3CoHsOT" 2H90, 50 g/liter NH4CI, 60 ml/liter NH4OH (28% NH3); temp. 80~

d ~ 4,o

2.0

0 4

I I I ~' I gl,~ 0 CONCENTRATION, s Jo ~ ...... 2-0SOD. HYPOPHOSPHITE(H20 ) CONCENTRATION,g/.~ 3 DMAB

Fig. 6. Effect of DMAB-hypophosphite combinations on electroless cobolt ploting rote from olkoline both. Both: 35 g/liter COSO4 9 7H20, 80 g/liter No3C6HsO~, 9 2H20, 50 g/liter NH4CI, 60 ml/liter NH4OH (28% NH3); temp. 80~

deposit on aluminum, b y t r e a t m e n t in zincate solution, is desirable for rapid, u n i f o r m coverage w i t h cobalt. Copper, brass, silver, platinum, titanium, o r stainless steels u s u a l l y do not initiate electroless cobalt deposition unless one of the following steps are t a k e n : (i) activation of the surface b y nucleation w i t h a catal y t i c a l l y active m e t a l such as p a l l a d i u m ; (ii) contact in the solution w i t h an a c t i v e l y p l a t i n g m e t a l ; (iiO m o m e n t a r y a p p l i c a t i o n of sufficient cathodic c u r r e n t to a p p l y a t h i n cobalt film electrolytically. Nonconductors a r e r e a d i l y p l a t e d after p a l l a d i u m activation (27). The effect of DMAB concentration on the p o t e n t i a l of electrolytic copper (99.9% p u r i t y ) in t h e cobalt plating b a t h is shown in Fig. 9. The p o t e n t i a l became m o r e negative w i t h i n c r e a s e d DMAB concentration, and though gassing was visible in all b a t h s containing DMAB, deposition was u s u a l l y not initiated. However, occasionally spontaneous initiation o c c u r r e d as illust r a t e d b y the d o t t e d line in Fig. 9 and has even occ u r r e d in t h e baths containing only 4 g / l i t e r DMAB.

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"CoL 12I, No. 8

ELECTROLESS COBALT DEPOSITION

1027

250

~ , , ~

Co-P (ALKALINE BATH)

~ 200
I.,.

[]

D---

~d

o 9 '~ 150 z

n,. - 0 . 8 LU a. P. o u .J z w o. - 0 . 4 -0.6 I I / I

/
I

PLATING INITIATED

_<

~
M. I00 0 I0 0
I I

Co-B (ACIDICBATH) ,9 C.,, Z' .., 0 Co-B (ALKALINE BATH)

I 2 ! 3 I 4

3-

O-

I 5

ELECTROLEBS COBALT OEPOSIT, mg/cm 2

-0.2

Fig. 10. Coercive force of electroless cobalt deposits produced from various baths. the hardness increased to 480 k g / m m 2. Additional heating at 250~ f u r t h e r increased the hardness to a m a x i m u m of about 640 k g / m m 2 after a total heating time of 4 days. Magnetic properties.--The coercive force of electroless cobalt deposits produced from three baths are shown i n Fig. 10. The coercive force of the cobaltboron deposits was constant, over the range of thickness tested, at about 8 oersteds. The coercive force of cobalt-phosphorus deposits was considerably higher and increased with decreasing deposit thickness.

0 0

t I

t 2

I ) I ) t 3 4 5 6 7 DMAB CONCENTRATION, g / ~

| 8

I 9

1 I0

Fig. 9. Effect of DMAB concentration on the steady-state potential of copper in electroless cobalt plating bath. Bath: 25 g/liter CoSO4" 7H20, 25 g/liter C4H4N~O4" 6H~O, 15 g/liter Na2SO~; pH 5.0; temp. 70~ The e x p l a n a t i o n for this p h e n o m e n a is not known, b u t catalytic particles that e n t e r the b a t h m a y provide the initiating influence b y chance contact. P l a t i n u m is more catalytically active t h a n copper, acquiring a potential of --0.54V in the 4 g a i t e r DMAB baths, but, as m e n t i o n e d earlier, did not initiate cobalt deposition. It was found that w h e n the succinate of the electroless cobalt plating b a t h of preferred composition was substituted by the e q u i v a l e n t molar q u a n t i t y of sodium malonate, deposition was more likely to be spontaneously initiated o n copper, and deposition rates were unaffected b y the substitution. It thus appears that the succinate has a n i n h i b i t i n g effect on the catalytic initiation of cobalt deposition o n copper and that m a l o n a t e can be used i n place of succinate i n the b a t h if spontaneous deposit initiation on copper is desired.

Corrosion prevention.--The results of salt spray exposure tests on electroless cobalt and nickel plated steel panels are shown in Table I. All of the electroless cobalt or electroless nickel deposits were quite protective to steel for up to 48 hr salt spray exposure. With longer exposure times, the protective value of the coatings increased with thickness. The electroless nickel deposits were somewhat more protective of steel t h a n cobalt deposits. However, edge corrosion was very pronounced with electroless nickel coated specimens while the electroless cobalt plated steel was resistant to edge corrosion. The corrosion potential of electroless cobalt-boron deposits, immersed in 50 g / l i t e r sodium chloride solution for 24 hr, was --0.60V (SCE). Steel and electroless nickel i n the s a l t solution have corrosion potentials of --0.63 and --0.35V, respectively. The p r o n o u n c e d edge corrosion encountered with electroless nickel plated steel is u n d o u b t e d l y the result of the adverse electrochemical relationship of the couple. The potentials would indicate cobalt a n d steel to be m u c h more galvanieally compatible in salt solution t h a n nickel and steel. From the corrosion potentials it can be predicted that a double l a y e r deposit of electroless nickel-phosphorus followed b y a topcoat of electroless cobalt-

Deposit properties.--Composition--The composition of electroless cobalt deposits from the preferred (2525-15-4) bath (pH 5.0, 70~ was d e t e r m i n e d to be: cobalt, 96.0% b y weight; boron, 1.7% b y weight; carbon, 0.97% by weight; a n d nitrogen, 0.05% b y weight. The presence of carbon and n i t r o g e n indicates organic or organometallic compounds in the deposit. Hardness.--Electroless c o b a l t - b o r o n deposits were found to have a hardness of 270 k g / m m 2 (Vickers) i n the as-plated condition. After heating 24 hr at 250~

Table I. Corrosion resistanceof electrolesscobalt or nickel plated steel

Deposit thickhess,/zm 3 S 10 3 6 12 C o r r o s i o n r a t i n g * a f t e r e x p o s u r e s to s a l t s p r a y , a v g of 3 24 h r 5 5 5 4 (E) 5 (E) 5 48 h r 4 5 5 4 (E) 5 (E) 5 (E) 72 h r 3 4 5 4 5 5 + (E) (E) (E) 3 3 5 3 5 5 96 h r (sl. E) + + (E) (E) (E) 168 h r 2 (E) 3 (sl. E) 3 + (sl. E) 2 + (E) 5 (E) 5 (E)

Deposit

Electroless Electroless Electroless Electroless Electroless Electroless

cobalt cobalt cobalt nickel nickel nickel

* R a t i n g s ( e x c l u d i n g e d g e s ) : 5 = n o basis m e t a l a t t a c k ; 4 = t r a c e s o f b a s i s m e t a l a t t a c k ; 3 = s l i g h t b a s i s m e t a l a t t a c k ; 2 = m o d e r a t e basis m e t a l a t t a c k ; 1 = considerable basis m e t a l a t t a c k . E = e d g e corrosion; sl. E = s l i g h t e d g e c o r r o s i o n .

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1028

J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
cobalt topcoat. A chromating t r e a t m e n t sistance of the cobalt to tarnishing. The presence of even small quantities phite i n electroless cobalt plating baths results i n m a r k e d reduction of deposition tion of deposition.

A u g u s t 1974
improves reof hypophoswith DMAB rate or cessa-

boron would p r o b a b l y provide synergistic protection because of the ability of the cobalt to sacrificially protect the nickel layer from corrosive penetration. This relationship with the synergistic protection of electrodeposited nickel double layers has been well established (28-30). Double layer deposits (7.5 ~m electroless nickel-2.5 ~m electroless cobalt) on steel were found capable of p r e v e n t i n g basis metal attack (even at edges) d u r i n g 168 h r salt spray exposure and were superior to the same total thickness of either layer alone.

Acknowledgment
The authors gratefully acknowledge the participation of Dr. A. Tauber, U.S. A r m y Electronics Command, Fort Monmouth, New Jersey, i n conducting the e x p e r i m e n t a l work involving magnetic m e a s u r e m e n t s of deposits. Manuscript submitted Oct. 29, 1973; revised m a n u s c r i p t received March 30, 1974. This was P a p e r 222 presented at the Miami Beach, Florida, Meeting of the Society, Oct. 8-13, 1972. A n y discussion of this paper will appear in a Discussion Section to be published in ~he J u n e 1975 JOURNAL. All discussions for the J u n e 1975 Discussion Section should be submitted by Feb. 1, 1975. REFERENCES 1. A. B r e n n e r a n d G. E. Riddell, J. Res. Natl. Bur. Std., 37, 31 (1946) ; Proc. Am. Electroplaters" Soc., 33, 23 (1946). 2. J. S. Sallo, Plating, 54, 257 (1967). 3. F. R. Morrall, ibid., 59, 131 (1972). 4. R. D. Fisher and W. H. Chilton, This Journal, 109, 485 (1962). 5. Y. Moradzadel% ibid., 112, 891 (1965). 6. L. D. Ranson a n d V. Zentner, ibid., 111, 1423 (1964). 7. J. G. Miksic, R. Travieso, A. Arcus, and R. H. Wright, This Journal, 113, 360 (1966). 8. J. S. Judge, J. R. Morrison, and D. E. Speliotis, ibid., 113, 547 (1966). 9. J. S. Judge, J. R. Morrison, D. E. Speliotis, and G. Bate, ibid., 112, 681 (1965). 10. R. D. Fisher and W. H. Chilton, Plating, 54, 537 (1967). 11. F. P e a r l s t e i n a n d R. F. Weightman, ibid., 54, 714 (1967). 12. J. R. DePew and D. E. Speliotis, ibid., 54, 705 (1967). 13. R. D. Fisher, IEEE Trans. Magnetics, 2, 681 (1966). 14. M. Soraya, Plating, 54, 549 (1967). 15. R. J. Heritage and M. T. Walker, J. Electron. Control, 7, 543 (1960). 16. J. Ragrowski and M. Lauriente, This Journal, 109, 987 (1962). 17. J. C. Hendy, H. D. Richards, and A. W. Simpson, J. Mater. Sci., 1, 127 (1966). 18. G. W. Lawless and R. D. Fisher, Plating, 54, 709 (1967). 19. A. B r e n n e r a n d G. E. Riddell, J. Res. Natl. Bur. Std., 39, 385 (1947); Proc. Am. EIectropIaters" Soe., 34, 156 (1947). 20. R. M. Hoke, U.S. Pat. 2,990,296 (1961). 21. T. Berzins, U.S. Pat. 3,338,726 (1967). 22. R. M. Lukes, PZating, 51, 969 (1964). 23. G. O. Mallory, ibid., 58, 319 (1971). 24. K. M. G o r b u n o v a a n d A. A. Nikiforova, J. Phys. Chem., USSR, 28, 883 (1954). 25. M. Schwartz, Proc. Am. Electroplaters' Soc. 47, 176 (1960). 26. F. Pearlstein and R. F. Weightman, Plating, 56, 1158 (1969). 27. F. Pearlstein, Metal Finishing, 53, 59 (1955). 28. M. M. Beckwith, Plating, 47, 402 (1960). 29. A. H. DuRose, Proc. Am. Electroplaters' Soc., 47, 83 (1960). 30. A. H. DuRose a n d W. J. Pierce, Metal Finishing, 57, 44 (1959).

Tarnish resistance.--Electroless cobalt-boron deposits

t a r n i s h r a p i d l y d u r i n g salt spray exposure to produce a tenacious, unattractive, mottled, b l u e - b r o w n film. Consideration was given to blackening the electroless cobalt deposits i n order to avoid the t a r n i s h i n g during salt spray exposure and also to provide a n o n reflective surface often desired for m i l i t a r y equipment. Some success was achieved in providing a blackened surface by immersion for 10 m i n i n 10 g a i t e r potassium persulfate solution at 25~ Immersion of electroless cobalt deposits i n a dichromate-sulfuric acid solution greatly improved the resistance of the surface to tarnishing; the surface rem a i n e d bright and u n t a r n i s h e d after 72 h r salt spray exposure. The solution was m i l d l y corrosive to the cobalt-boron, removing about 0:I #m d u r i n g the 10 sec immersion. No visible film was produced b y the t r e a t ment. The proprietary chromating solution was n o n c o r rosive to the electroless cobalt and also substantially improved resistance to t a r n i s h i n g though not quite as effectively as the other solution. Longer immersion times (e.g., 30 sec or more) in the proprietary solution resulted in the i m p a r t i n g of a visible iridescent film that provided i m p r o v e m e n t of the deposit in resistance to basis metal corrosion during salt spray exposure. The chromate t r e a t m e n t s described above m a y be valuable for application to thin, magnetic, electroless cobalt deposits since even slight atmospheric corrosion can significantly alter the magnetic properties (9).

Conclusions
A n acid electroless cobalt plating bath at pH 5.0 of the following composition is capable of producing bright deposits (96.0% Co, 1.7% B, 0.97% C, 0.05% N) at a rate of about 13 ~ m / h r at 70~ 25 g / l i t e r cobalt sulfate ( C o S O 4 . 7 H 2 0 ) , 25 g / l i t e r sodium succinate (C4H4Na204 9 6H20), 15 g / l i t e r sodium sulfate (Na2SO4), and 4 g / l i t e r d i m e t h y l a m i n e borane [ (CH3)2HNBH3]. Steel, electroless nickel, gold, a l u m i n u m (zincate treated), or p a l l a d i u m - a c t i v a t e d nonconductors sloontaneously initiate electroless cobalt deposition from the acid bath; copper, silver, brass, or p l a t i n u m u s u a l l y do not initiate deposition. The hardness of as-plated electroless cobalt deposits is 270 k g / m m 2 (Vickers) and can be increased to 640 k g / m m 2 b y heating at 250~ The coercive force of cob a i t - b o r o n deposits are relatively low at about 8 oersteds. Electroless cobalt deposits can provide effective protection for steel against corrosive attack. Synergistic protection is provided b y a double layer deposit consisting of electroless nickel-phosphorus and electroless

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