Microelectronic Engineering 50 (2000) 525531

www.elsevier.nl / locate / mee

Electrochemically deposited thin film alloys for ULSI and MEMS

applications
Y. Shacham-Diamand*, Y. Sverdlov
Department of Physical Electronics, Tel-Aviv University, Ramat-Aviv, 69978, Tel-Aviv, Israel
Abstract
Thin metal films can be electro-deposited for interconnect metallization and packaging. Electro-forming offers unique
properties, such as excellent filling of high aspect ratio structures, unique compositions, low temperature processing and low
stress films. Electroless forming offers also high selectivity. Binary and ternary metallic alloys, such as Ni, Co and Cu,
alloyed with iron, phosphorous, boron and refractory metals have been demonstrated to form conducting layers, barriers, and
corrosion protection layers. High quality very thin films, with thickness varied between 5 nm and 1 mm, have been
demonstrated with good composition control. After reviewing the basic deposition mechanisms we focus on Co and Ni
alloys with refractory metals (e.g., tungsten and molybdenum) and with phosphorous and / or boron. We present results of
electroless deposition of CoWP as examples for an electrochemical process compatible with silicon technology. Finally we
present a process outline for alloy deposition on silicon, or SiO 2 , for MEMS applications. 2000 Elsevier Science B.V.
All rights reserved.

1. Introduction
Electro-deposition of metals has a wide use in microelectronics, especially in packaging and
printed-circuit board applications. Recently the use of copper has been demonstrated for very
large-scale integration (VLSI) using either electro-plating [1] or electroless plating [2]. At first glance,
electro-plating seems to be a very simple technology; metal ions receive one or more electrons and are
deposited from a solution. In reality, the electro-deposition process is quite complex and the solution
includes, in addition to the metal ions, various additives that play a significant role in the metal thin
film properties [3,4]. Electroless deposition is similar to electro-plating in the sense that the metal is
reduced electrochemically. However, the electrons are the result of other chemical processes in the
solution and there is no external current [5]. Electroplating has been used for the deposition of alloys
[5] with very interesting properties. Since electro-deposition can occur at very fast rate, it is possible
to operate at a regime where the adatoms do not reach their equilibrium position at the surface.
Therefore, alloys that traditionally are stable at high temperature only can be produced electro*Corresponding author. Fax: 1972-3-642-3508.
E-mail address: yosish@eng.tau.ac.il (Y. Shacham-Diamand)
0167-9317 / 00 / $ see front matter
PII: S0167-9317( 99 )00323-8

2000 Elsevier Science B.V. All rights reserved.

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Y. Shacham-Diamand, Y. Sverdlov / Microelectronic Engineering 50 (2000) 525 531

chemically at room temperature. For example, amorphous Ni and Co alloys, which traditionally were
produced by quenching from high temperature, can be produced by electro-deposition [6]. Under most
circumstances, elemental deposition is micro-crystalline. On the other hand, binary and ternary
electro-deposited alloys can be either crystalline or amorphous.
In this paper we present the basic theory of electro-deposition of ternary alloys that contain atoms
of noble metals (Cu, Ni, Co or Ag), refractory metals (W, Re or Mo), and either phosphorous or
boron. As examples we describe the electroless deposition of cobalt (or nickel) tungstenphosphorous (CoWP or NiWP) on silicon and silicon dioxide. In most applications, copper is used as an
interconnect material and CoWP and NiWP are used for adhesion, barrier and capping layers. Such
layers can be applied for ULSI interconnects MEMS and micro packaging of ULSI, i.e., flip chip
technology using BGA and chip scale packaging (CSP). Another application is the coating of MEMS
components for high-frequency applications. The coating is required to improve surface conductivity
of silicon-based components for RF applications. CoWP and NiWP were preferred over CoP and NiP
since the added refractory metal increases hardness and melting point. Therefore, electroless CoWP
was tested as barrier against copper [7,8]. CoWP and NiWP also have better adhesion to silicon and
silicon dioxide than Cu. On the other hand, Cu adheres very well to CoWP and NiWP. Therefore,
CoWP and NiWP serve also as adhesion layers between Cu and silicon or silicon dioxide. This effect
also can be electrochemical because the reduction potential of copper is 0.34 eV versus standard
hydrogen electrode (SHE) and that of Ni and Co is about 2 0.26 eV (SHE). It also can be due to the
poor quality of copper oxides that always exist between copper and silicon.
2. Theory of alloy electro-deposition
Basic alloy electro-deposition has been described traditionally as a simultaneous deposition of two
or more components from the solution [3,4,9]. The components are reduced at the surface and the
alloy composition is determined by the relative ratios of the fluxes of the various components. The
galvanic potential between the cathode and the solution is the same for all the deposited components.
Therefore, the various fluxes of the electrodeposited components can be deducted from the current
potential curve of each component separately (Fig. 1). Each of the components follows the
conventional deposition process: (a) transport from the solution to the surface and (b) electronation of
the species at the metalsolution interface. Therefore, the current density of the xth component can be
either limited by diffusion:
Dx nFC 0x
j x 5 2 ]]]
d

(1)

where Dx is the diffusivity, n is the ion charge, F is the Faraday constant, C 0x is the concentration of
the component in the solution and d is the diffusion layer thickness. The reaction can be limited by
the surface reaction rate (high-field Butler Volmer equation):
j x 5 j 0,x ? e 2 ax Fh / RT

(2)

where J0,x is the surface exchange current, a is the activity, h the overpotential and T is the
temperature. The total current is equal to the external current, in the case of electrodeposition, or to
the anodic current due to the oxidation of the reducing agent in electroless deposition.

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527

Fig. 1. Current versus overpotential curves of deposition of three metals: (1) with the highest equilibrium potential; (2)
lower E0 and lower transport limited current (1); and (3) lower E0 and higher transport limited current (examples: Case A,
J1 . J2 , J3 50; Case B, J3 . J1 . J2 ).

This theory is correct as long as the various components are deposited via a pure electrochemical
process on the cathode. This is typical when the metal is in an ionic state in the solution and can be
deposited independently. This is not always the case, especially for the codeposition with refractory
metals or with phosphorous or boron. In this case the co-deposition is a mixture of an electrochemical
process on the cathode and a chemical process in the solution that is accompanied to that process. For
example, the deposition of a noble metal (Ni, Co, Cu, etc.)refractory metal (W, Mo, Re, etc.) alloy is
assumed to have two parallel processes [10]. The first is the reduction of the metal complex with
negative charge of 2n (for example citrate ion, which is frequently used for cobalt and nickel, has
n53).
Electrodeposition current of the noble metal, M1, complex:
[M1 ? Cmplx] 22n 1 2e 2 M1 0 1 Cmplx 2n

(3)

where we assume that the metal ion charge is 12. This reaction generates a flux J M1,1 of M1 to the
0
surface. JM1,1 is proportional to the concentration, C M1
, of M1 in the solution.
The second step is the reduction of the refractory metal ion via the intermediate [M1?Cmplx?
M2O 4 ] 2n complex. This step can follow either homogeneous or heterogeneous intermediate reactions.
Both reactions generate a flux, JM2,2 of refractory metal ions and, JM1,2 , of M1. Both currents are
proportional to C 0M1 3C 0M2 . Note, that for baths with hypo-phosphoric or di-methyl-amine-borane
there are also additional reactions that are responsible for a third flux, JM3 , of phosphorous or boron
into the alloy. Therefore, we assume that the composition of M2 in the metal for binary deposition is
given by the ratio of JM2 to the total flux:
0

solid
M2

JM2
A 2 ? C M1 ? C M2
5 ]]]]] ]]]]]]]]]]
~C 0M2 u JM1 . JM2 , JM3
0
0
0
JM1 1 JM2 1 JM3 A 1 ? C M1
1 A 2 ? C M1 ? C M2 1 JM3

(4)

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Y. Shacham-Diamand, Y. Sverdlov / Microelectronic Engineering 50 (2000) 525 531

Note, that this expression is an approximation where we neglect the differences in the terms that
contain the overpotential. The homogeneous intermediate reaction may start with the formation of a
double metal complex:
M1 ? Cmplx 22n 1 M2O 422 [M1 ? Cmplx ? M2O 4 ] n

(5)

The deposition of the refractory ions is completed via a catlytic reaction with the noble metal ion.
[M1 ? Cmplx ? M2O 4 ] 2n 1 4H 2 O 1 6 e 2 M2 0 1 M1 ? Cmplx 22n 1 8OH 2

(6)

The heterogeneous reaction takes a similar path, however, it generates species that are adsorbed to the
surface of the deposited film:
M1 ? Cmplx 22n 1 M2O 4 22 1 2H 2 O 1 2e 2 [M1 ? Cmplx ? M2O 2 ] ads 22n 1 4OH 2

(7)

And deposit the refractory metal via a catalytic reaction with the other metal, M1.
[M1 ? Cmplx ? M2O 2 ] 22n 1 2H 2 O 1 4 e 2 M2 0 1 M1 ? Cmplx 22n 1 4OH 2

(8)

The cathodic current is balanced by an external current or by the anodic current due to the oxidation
of the reducing agent. For example, we use H 2 PO 2
2 for CoWP and NiWP deposition. In this case the
general reaction is:
2
1
2
H 2 PO 2
2 1 HOH H 3 PO 3 1 2H 1 2 e

(9)

3. Electroless deposition of nickel and cobalt alloys

We present the electroless deposition of nickel and cobalt alloys as an example for the application
of alloy electro-deposition for ULSI and MEMS. Thin films of the ternary alloys, CoWP or NiWP,
were deposited from solutions that contain metal sulfate, hypo-phosphate ions, citrate, and tungstate
ions. To improve deposition we added either boric acid or ammonium chloride. We also added
surfactant, GAF-RE610, to improve wetting which is important for deposition on sub-micron features.
The deposition occurs at temperatures in the range of 75908C and at pH levels of 7.59. The
pre-deposition procedure included cleaning and surface activation. Prior to deposition the samples
cleaned by HCl:H 2 O 2 at 808C for 15 min followed by NH 4 OH:H 2 O 2 (2:1) at 808C. Next, the samples
were dip-etched in buffered HF and rinsed well in H 2 O. Surface activation was required to initiate the
self-catalytic electroless deposition. We used both wet (dip in PdCl 2 :HCl solution) and dry activation
methods (sputtered seed) [7,8].

3.1. Results: electroless CoWP deposition

The following results refer to the solution Co-2 that contains 23 g / l of CoSO 4 ?6H 2 O, 31 gr of
H 3 BO 3 , 21 g / l of NaH 2 PO 2 , 130 g / l of Na citrate, 030 g / l of Na 2 WO 4 ?2H 2 O and 0.05 g / l
surfactant. The composition of tungsten in the alloy was measured as a function of the tungstate ion

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529

concentration as the cobalt ion concentration remained constant. We found that the tungsten
concentration is proportional to that of the tungstate ion concentration in the solution (Fig. 2).
The deposition rates for the films increased with temperature. For example, the solution Co-2 with
10 g / l of deposited CoWP at a rate of 4045 nm / s at 808C and 6065 nm / s at 908C. The deposition
rate of films on wet activated surfaces was significantly higher at the first 60 s.
The deposition rate was measured as a function of the concentration of its various components. We
measured the deposition rate for the solution Co-2 with 10 g / l of Na 2 WO 4 ?2H 2 O and various
concentrations of reducing agent NaH 2 PO 2 . It was found that when the molar concentration of
Na 2 WO 4 ?2H 2 O larger than that of the cobalt ion the deposition rate is independent of the reducing
agent, while for lower concentrations the deposition rate drops. We also measured the deposition rate
of the solution Co-2 with with 10 g / l of Na 2 WO 4 ?2H 2 O and 21 g / l of NaH 2 PO 2 of various dilutions

Fig. 2. The atomic concentration of tungsten in the solid as a function of ratio of concentration of the tungstate ion to that of
the cobalt ion in the solution.

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in DI water (keeping the pH constant at about 9). It was found that the deposition rate decreases from
about 7080 to about 20 nm / min. for the 1:10 dilution.

3.2. Electroless deposition of CoWP for MEMS and VLSI applications

CoWP thin films were deposited for two applications:
1. for VLSI interconnects (in the structure of CoWP/ Cu / CoWP on oxide [7]);
2. for MEMS (as CoWP or CoWP/ Cu / CuWP) on Si or SiO 2 [8].
CoWP could be deposited on wet or dry activated surfaces. CoWP could also be directly deposited
on Cu using Zn or Al initiation that starts the electroless CoWP deposition on Cu surface and the
autocatalytic reaction. In this process we touch the samples with Al or Zn wires. Zn and Cu (and also
Al and Cu) form a galvanic cell that supplies the electron current for the reduction of Co. Once Co is
deposited, the reaction continues due to its self-catalytic characteristic. For example, the Al effect can
be summarized as follows:
Anodic reaction: Al 0 Al 31 1 3e 2

(10)

2
0
0
2
Cathodic reaction: Co 21 1 H 2 PO 2
2 1 3e Co 1 P 1 2OH

(11)

Using his reaction CoWP and CoWP/ Cu / Co thin films were deposited on MEMS structure. The films
were deposited on silicon beams that had been released by the SCREAM process (Fig. 3). The
conducting thin film alloy was required to increase the surface conductance of the beam for making
switches or high-frequency components.

4. Discussion and conclusions

Nickeltungstenphosphorous and cobalttungstenphosphorous was deposited for MEMS and
ULSI applications. Similar thin films with molybdenum or rhenium can also be deposited with
phosphorous or, alternatively, boron. All this materials open new opportunities for new structures for
VLSI and MEMS. Electro-forming is a very cost-effective process with the ability to form unique
alloys with excellent quality. The very conformal or even super conformal coating of electroplating or
electroless plating with special additives makes this technology important for deposition on small
features with high aspect ratio. The fact that it allows temperature and low stress film is important for
MEMS structures that are integrated with CMOS.
The exact mechanism of the tungsten deposition is still under study. It is clear that the tungsten is
carried by some reaction with the cobalt ions. It was demonstrated that the tungsten concentration
increases as the cobalt ion concentration increases in the solution. This reaction is going in parallel
with the cobalt reduction reaction in the electroless deposition. The role of the phosphorous in the
tungsten deposition is not clear yet.

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531

Fig. 3. Selective deposition of electroless metal on silicon beams. The beam must be isolated from the substrate or coated
with thin oxide.

Acknowledgements
The work was supported by a grant from the Israeli Ministry of Science and Technology.
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