Professional Documents
Culture Documents
net/publication/313099862
electrodeposition
CITATIONS READS
0 2,754
1 author:
P S Rama Sreekanth
National Institute of Science and technology
52 PUBLICATIONS 166 CITATIONS
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
At present i am working on polymer composites for electrical, mechanical and sensor applications .Thank for your interest View project
All content following this page was uploaded by P S Rama Sreekanth on 31 January 2017.
This article was originally published in the Reference Module in Materials Science and Materials Engineering
published by Elsevier, and the attached copy is provided by Elsevier for the author’s benefit and for the benefit of the
author’s institution, for non-commercial research and educational use including without limitation use in instruction
at your institution, sending it to specific colleagues who you know, and providing a copy to your institution’s
administrator.
All other uses, reproduction and distribution, including without limitation commercial reprints, selling or licensing
copies or access, or posting on open internet sites, your personal or institution’s website or repository, are prohibited.
For exceptions, permission may be sought for such use through Elsevier’s permissions site at:
http://www.elsevier.com/locate/permissionusematerial
Losey, M.W., Kelly, J.J., Badgayan, N.D., Sahu, S.K., and Rama Sreekanth, P.S. (2017) Electrodeposition. In:
Saleem Hashmi, Reference Module in Materials Science and Materials Engineering. vol. 13, pp. 1–20. Oxford:
Elsevier.
Electrodeposition$
MW Losey, Touchdown Technologies, Baldwin Park, CA, USA
JJ Kelly, IBM/TJ Watson Research Center, Yorktown Heights, NY, USA
ND Badgayan, SK Sahu, and PS Rama Sreekanth, National Institute of Science and Technology, Berhampur, India
r 2017 Elsevier Inc. All rights reserved.
1 General Principles 1
1.1 Kinetics 2
1.2 Principles of Alloy Deposition 3
1.3 Methods 4
1.3.1 Thickness uniformity 4
1.3.2 Throwing power 5
1.3.3 Bubbles 5
1.3.4 Pulse plating 6
1.3.5 Multilevel microfabrication with electrodeposition 6
1.4 Patterned Electrodeposition 7
1.4.1 Workpiece and pattern scale effects 8
1.4.2 Feature scale effects 8
1.4.3 Summary: Uniformity at the workpiece, pattern, and feature scales in LIGA 11
2 Properties of Electrodeposits 12
2.1 Internal Stress 12
2.2 Adhesion 12
2.2.1 Electroplating on aluminum 13
2.3 Crystal Orientation and Microstructure 13
2.4 Mechanical Properties of Electrodeposits 13
2.4.1 Tensile test 13
2.4.2 Hardness 14
2.4.3 Bulge test 14
2.4.4 Origins of strength 14
2.5 Thermal Stability 15
3 Selected Metals and Applications 15
3.1 Nickel and Nickel Alloys for Mechanical Actuation 15
3.2 Copper for RF MEMS and Electrical Interconnects 17
3.3 Gold 17
3.4 Thermoelectric Thin-Film Microdevices: Bi2Te3 18
4 Conclusion 19
References 19
☆
Change History: January 2016. N.D. Badgayan, S.K. Sahu, and P.S. Rama Sreekanth modified Abstract, refined Keywords, expanded text with additional review
materials, added conclusion, and amended references.
1 General Principles
The electrodeposition of metals, alloys, and semiconductors has found broad use in the fabrication of microsystems and
microelectromechanical systems (MEMS). While a large number of metals found in microsystems can be electroplated from
aqueous electrolytes (Ni, Cu, Au, Pt, Fe, Pb, to name a few), a few metals cannot, notably Al, Ti, and pure W. Nickel and its high-
strength alloys constitute some of the more useful materials available to microsystem fabrication by electrodeposition, owing to
their use in forming mechanical and magnetic elements such as precision gears, latches, motors, and flexure spring arms (Malek
and Saile, 2004). Electroplating is a versatile technique spanning the range of coatings and thin films less than a micron to thick
electroformed mechanical elements millimeters tall. Materials are deposited near ambient conditions without the need for
expensive vacuum equipment. Deposition rates can be much faster than vapor deposition methods and film thicknesses can be
as high as a millimeter or two. The essential elements of the process are the cathode, or the workpiece to be plated, an anode or
counter electrode, and an electrolyte that possesses the metal ion in reducible form. Current is supplied to the workpiece, which for
MEMS is often a flat substrate metallized by vapor deposition. This thin metal coating forms a conductive seed layer to which
electrical contact is made. The seed layer can cover micropatterned films of insulator, as in the copper Damascene process for
integrated circuit interconnects. Or, an insulating, patterned layer for through-resist plating can mask the seed layer. The latter
approach is more often utilized for making freestanding parts, exemplified by the LIGA (lithographie, galvonoformung,
abformtechnik, German acronym associated with the process of lithographically defining molds for electroforming) and X-ray
lithographic methods. The use of LIGA process overcomes many drawbacks of traditional fabrication methods and pattern transfer
technique such as chemical etching, sputter etching, reactive ion etching.
In this chapter, some of the fundamentals of electrodeposition are reviewed first; there are numerous references that provide far
more detail (Bard and Faulkner, 2001; Dini, 1993; Lowenheim, 1995; Schlesinger and Paunovic, 2000). In addition to kinetics,
some general methods (including common issues) are detailed to give the MEMS practitioner a starting point for conducting an
electrodeposition process. Some of the ramifications of plating through lithographically generated patterns are discussed. Although
there is a rich literature and much recent progress has been made on the modeling and simulation of patterned electrodeposition,
that topic is beyond the scope here. Instead, we cover some of the general principles and focus on the properties and processes of
electrodeposits most relevant for MEMS. Finally, an assortment of materials, recipes, and applications are provided as a starting
point for electrodeposition for MEMS, with emphasis on nickel and its alloys for application to micromechanical elements.
1.1 Kinetics
The rate at which a metal is deposited is related to the current density by Faraday’s law, which states that the extent of an
electrochemical reaction that occurs is proportional to the electrical charge passed. Each metal has an electrochemical equivalent Z,
or the proportionality constant relating deposition rate to current density. For example, the growth rate can be expressed as
follows:
Z CE J
Rate mm h1 ¼ 3:6 104 ½1
r
where CE is the current efficiency, J is the current density (in mA cm2), r is the density of the metal (in g cm3), and
M
Z¼ ½2
nF
where M is the molecular weight (in g mol1), n is the number of electrons involved, and F is Faraday’s constant, 96 485 C mol1.
For the case of nickel electrodeposition Ni2 þ , n¼2, M¼ 58.71 g mol1, Z ¼ 3 104 g C1, and the linear growth rate
(r¼8.9 g cm3) at a current density of 10 mA cm2 is 11.5 mm h1, assuming the CE is 95%, which is typical for Ni. The CE is the
ratio of charge consumed toward the deposition reaction to the total charge consumed. Side reactions, such as the reduction of
hydrogen, detract from the CE. Copper electrodeposition usually has nearly 100% CE with current densities up to 50 mA cm2.
Nickel electrodeposition generally has 95–100% CE, but unlike copper, CE will drop at current densities lower than 3 mA cm2 CE
for gold electrodeposition can be as low as 50%, depending on the bath formulation.
The upper limit to the rate of metal deposition is determined by the mass transport, or diffusion, of the metal ion species to the
cathode surface. In the case of a planar surface with no convection or mixing of the electrolyte, the current decreases with time as
metal ions are consumed near the vicinity of the electrode. For this case, the time-varying current density is described by the Cotrell
equation,
nFD1=2 C
jðt Þ ¼ ½3
p1=2 t 1=2
where D is the diffusion coefficient for the electroactive metal species and C is the concentration of the metal in the bulk solution.
Author's personal copy
Electrodeposition 3
Eventually, as the metal ions are consumed at the cathode surface, the deposition rate, or current density, becomes limited by
the rate of diffusive flux of ions to the surface. When the length scale for diffusion, δ, is known, such as the height of a resist feature
or for a rotating disk electrode, the limiting current can be described by
zFDC
jL ¼ ½4
δ
For extreme cases of resist height (4100 mm) and plating rates, it has been shown that natural convection can be a significant
component of the mass transport (Nilson and Griffiths, 2003). Under these conditions, the limiting current can be larger than that
expected by diffusion alone.
For a rotating disk electrode (the preferred tool of the electrochemist and the arrangement in many commercial electro-
deposition tools), the diffusion layer thickness, δ, can be precisely described and the limiting current is described by the Levich
equation,
0:62nFD2=3 o1=2 C
jL; RDE ¼ ½5
n1=6
where j0 is the exchange current density, a is known as the transfer coefficient, and Z is the overpotential or the difference between
the applied potential and the equilibrium potential. The first term refers to the cathodic process and the second term refers to the
anodic process. For irreversible electrochemical processes where the cathodic overpotential is large, the anodic component is
negligible and the Butler–Volmer equation reduces to the Tafel equation:
Z ¼ a þ b log j
2:3RT
a¼ log j0
aF
2:3RT
b¼ ½7
aF
A Tafel plot (log i versus Z) is used to extract these kinetic parameters and glean insight toward the nature of the kinetic steps
involved.
In describing the overpotential, the equilibrium potential Eeq is related to the concentration of the electroactive species by the
Nernst equation, which for the reduction of a metal to its solid in an ideal solution is:
RT
Eeq ¼ E0 þ In C ½8
nF
Metals whose equilibrium potentials differ significantly can still be made to codeposit by reducing the activity of the more
noble metal. The classic example is Cu–Zn, where the equilibrium potentials are considerably different (Cu ¼ þ 0.342,
Zn¼ 0.762). In electrolytes of the simple salts, alloy deposition is impossible, as copper will deposit to the virtual exclusion of
zinc. However, Cu–Zn alloys are readily plated using electrolytes where the copper species is complexed, typically as a cyanide.
Unfortunately, one of the most useful alloys for MEMS, Ni–Fe (and Ni–Co), falls in the category of anomalous codeposition. In
this category of abnormal alloy electrodeposition, the less noble metal, iron, preferentially deposits and the alloy content does not
prescribe to the usual equilibrium potential relationships (Ni ¼ 0.257, Fe¼ 0.447). For this reason, the iron concentration in
the bath is much lower than nickel and the process is highly sensitive to mass transport and mixing effects.
Another category of abnormal alloy deposition is induced codeposition, where one element is codeposited as a result of the
catalytic activity or reduced overpotential of the alloy surface. Tungsten and molybdenum are examples of metals that can be
electrodeposited as part of an alloy, but not as a pure metal, Ni–W being the example relevant to MEMS. Ni–W has many desirable
properties including high hardness, improved corrosion and wear resistance, and thermal stability owing to the high melting point
of tungsten. Historically, Ni–W has been difficult to process owing to the high temperatures (80–90 1C) and high pH (8–11)
required of the electrolyte. Recent work involving a sulfamate electrolyte has better enabled integration into a MEMS process flow
(Slavcheva et al., 2005).
For the case of Ni–Mn (Ni ¼ 0.257, Mn¼ 1.18), the manganese content is very low as expected, usually less than 1 wt.%. In
fact, given the large difference in equilibrium potentials and the lower manganese concentrations in the electrolyte used (see
Table 2), it is surprising that any manganese is codeposited. It has been argued that manganese is incorporated as a result of
adsorption onto the nickel surface rather than a codeposition reaction (Atanassov and Schils, 1999). This is consistent with the
observed grain-refining effect that the manganese has on the resulting film.
The overall plating process can be summarized in following enumerated points
1.3 Methods
Electroplating can be a simple laboratory exercise involving a beaker and a power supply or an elaborate operation with means
for agitation, filtration, electric field shaping, temperature control, and multistep or pulsed current programs. As a matter
of practicality, most industrial electroplating processes are galvanostatic, rather than potentiostatic. This obviates the need
for a reference electrode and the variation in resistance that may occur as a result in subtle differences in cell configuration. The
current may either be direct or pulsed. It is common practice for substrates to be immersed hot, that is with potential applied
and current initiating immediately upon entry. This prevents any dissolution or deleterious oxidation of the seed by the
electrolyte media.
Figure 1 Overplating features increases surface area and reduces the overall current density, changing the properties of the deposit.
To describe the relative influence of these various resistances, a dimensionless Wagner number (Wa) is often employed
dZ=dJ
Wa ¼
re L
which in this case describes the relative influence of the polarization resistance, or the inherent resistance of the charge transfer
reaction, to the electrical resistance of the electrolyte and re is the electrolyte resistivity, and L is a characteristic length for
conduction. For Wac1, indicating that polarization resistance dominates, the current distribution is uniform and the secondary
current distribution is said to predominate. For Wao1, the primary current distribution predominates, that is the current density is
a result of the potential distribution of the cell.
In the cases where polarization resistance is relatively insignificant and the cell geometry dictates the potential field, numerous
approaches have been used to improve the current density distribution. One way is to insert an insulating barrier at the cathode, or
a cathode shield, to help shape the field lines and direct the current toward or away the center of the substrate. Another common
approach is to add auxiliary features (known as a robber or current thief) at the edge of the substrate to absorb the nonuniformity
intrinsic to any edge. Furthermore, sacrificial auxiliary features can be used to improve the area density, by provided isolated
features of a pattern with neighboring areas. The size and placement of the auxiliary electrodes may vary as well: larger areas may
be required at the substrate edge to direct current. Yet another approach is to provide multiple anodes, each with individual current
or potential current to provide real time shaping of the current distribution. With even more complexity, the cathode itself can be
divided into multiple current paths. Each approach has its own merits unique to the pattern and application, as well as level of
complexity and as a result all are found in industrial practice.
1.3.3 Bubbles
With patterned substrates, particularly with thick resists (10–100 mm) and high aspect ratio structures, surface tension and wetting
effects predominate. Generally, lithographically patterned substrates are dried in between processing steps and require wetting of
the features to provide electrolyte to the conducting metal surface. Bubbles that become trapped within resist features during this
initial wetting result in voids in the final metal, as the growing electroplating surface will envelope the bubble. Successful wetting is
highly dependent on the geometry and aspect ratio of the features, in addition to the state of the metal seed layer and the
hydrophobicity of the resist. If typical approaches such as rinsing or agitation are unsuccessful, extreme measures such as
evacuating the resist and immersing under vacuum can work for most cases. Bubbles can be formed as a result of incomplete
Author's personal copy
6 Electrodeposition
wetting of the initially dry surface, or can be generated during plating as a result of side reactions like hydrogen reduction. Nickel
electrodeposition, where the CE is usually less than 100%, can generate sufficient hydrogen to form bubbles. For this reason, the
nickel electrolytes are either operated at elevated temperatures or contain a surfactant (sodium lauryl sulfate) to reduce the surface
tension. Depending on the nature of the substrate, the initial stages of electroplating can be particularly prone to hydrogen
generation. Initiating metal deposition onto the substrate may require an additional overpotential due to the fact that it is a
different metal surface or that it possesses a thin oxide layer; the hydrogen overpotential itself may be reduced for the substrate
metal, such as the case for nucleating nickel on copper.
Figure 2 Multilevel structure fabrication by electrodeposition. Step 1: lithographically pattern resist on conductive substrate and electroplate
structural metal. Step 2: remove resist and electroplate sacrificial metal such as copper to fill and cover structural elements. Step 3: planarize to
desired thickness of the structural metal. Step 4: repeat steps 1–3, aligning to the previous level. Step 5: selectively etch the sacrificial metal to
provide multilayer elements attached to the substrate.
Author's personal copy
Electrodeposition 7
function is to provide a conductive base to initiate electrodeposition of the subsequent level. This eliminates the restriction of
plating on the structure exclusively and enables the creation more complicated by nearly 3D components.
Figure 3 Schematic illustration of the workpiece, pattern, and feature scales, redrawn from a similar graphic from DeBecker and West. Groups of
features are distributed across the substrate; these groups consist of a patterned array of features. The feature scale involves a single feature and
its internal uniformity.
Author's personal copy
8 Electrodeposition
electrodeposition processes for thin and thick resists, we will keep in mind that the materials that are deposited into these
lithographic molds may have very different deposition characteristics as well.
scale electrodeposition problem is the case of copper Damascene electrodeposition for copper interconnects. For this process,
proprietary electrolyte bath additives and active feature sidewalls lead to more complicated feature filling behavior, despite the fact
that only a single elemental species is being deposited. In the case of electrodeposition through thick resist for LIGA, the
importance of the feature scale is not its influence on the local deposit thickness uniformity (the wafer is planarized after plating,
removing thickness variations across the wafer at all scales). Rather, it is the more serious issue of poor mixing in the mold features
themselves due to their small widths and large heights. This has broad implications with respect to the potential for variations in
the concentrations of electrolyte species that may, in turn, impact the local deposit composition, morphology, and properties. For
example, if additives or other metal species are present as alloying elements, profound changes may occur through the thickness
owing to the constantly changing feature geometry that accompanies the metal growth. If the concentration of one of these species
is close to zero at the feature bottom (e.g., due to its rapid incorporation into the deposit), large changes in the flux of this species
will occur as the deposit grows and the diffusion length from the bulk electrolyte shortens. The resulting nonuniform deposit
morphology or alloy composition may be unacceptable for some applications. The electrodeposition of the NiCo and NiMn
systems and the resulting feature scale uniformity will be contrasted to demonstrate the importance of transport into LIGA features
later in the chapter.
Interesting experiments involving the feature scale were carried out by Leyendecker et al. (1994). These authors studied the
effect of thick photoresist on mass transport and on the pH within a LIGA feature using special electrodes. In the first series of
experiments, a rotating disk electrode masked by an insulating patterned polymer layer of various thicknesses and feature sizes is
employed to study a model redox reaction occurring under transport control. The aqueous electrolyte consists of 2 mM potassium
ferro- and ferricyanide each in 1 M potassium chloride at 25 1C. Results of their experiments are reproduced in Figure 4; although
various geometries were investigated, they present results for a constant hole diameter of 200 mm and resist heights of 100, 200,
and 500 mm (in addition to an unmasked electrode).
Another series of experiments relevant to the feature scale in LIGA involving transport limitations is reported (Griffiths et al.,
1998). They used a commercial Ni sulfamate electrolyte to deposit Ni into features drilled into PMMA. A single piece of Cu foil
attached to one side of the PMMA acted as the substrate, from which the deposited Ni structures could be removed for weighing in
the determination of the CE. Current densities ranged from 1.1 to 108 mA cm2. The drilled holes had diameters of 1.7, 3.2, and
6.4 mm and depths from 17 to 42 mm. They calculated the Sherwood number (the ratio between the measured current to the
diffusion-limited current) for each case. The experimental results are surprising in that the Sherwood numbers are all between 10
and 100, indicating a much larger deposition current than expected based upon the diffusion-limited case.
The authors explain the unexpectedly high currents as resulting from enhanced transport of the reacting metal ion due to
natural convection in the feature driven by its depletion at the substrate. This hypothesis is further supported by the fact that when
the experimental cell was inverted, the measured currents were an order of magnitude less than with the deposition surface facing
up. These authors go on to demonstrate by numerical modeling that flow across the top of the features cannot support the
transport of the reacting metal ions at the observed rates, and that instead buoyancy-driven flows are probably important in
allowing such high deposition rates. Nilson and Griffiths (2003) study natural convection in small features with respect to LIGA
Figure 4 Limiting current densities for ferri–ferro cyanide redox couple on bare and patterned rotating disk electrodes adapted from Leyendecker
et al. (1994). Feature hole diameter is 200 mm. The presence of the resist has a large effect on the transport of species to the feature bottom, even
for an aspect ratio of one. Solid points are the bare rotating disk electrode, while the hollow points are electrodes patterned with resists of various
thicknesses as indicated. Reprinted from Leyendecker, K., Bacher, W., Stark, W., Thommes, A., 1994. New microelectrodes for the investigation of
the electroforming of LIGA microstructures. Electrochim. Acta 39, 1139–1143, with permission from Elsevier.
Author's personal copy
10 Electrodeposition
electrodeposition. They find that the relative importance of natural convection depends on the feature geometry and the incli-
nation of the substrate. The authors conclude that some mixing from natural convection is expected to occur in features having
aspect ratios less than 1.2, 6.6, and 37 for resist thicknesses of 0.1, 1.0, and 10 mm, respectively. Thus, natural convection becomes
important for a wider range of feature aspect ratios as the resist thickness increases. Because resist thicknesses in microelectronics
are usually only tens of microns or less, the importance of convective flow had not been widely discussed until electrodeposition
into deep LIGA features was considered. It is interesting to contrast the findings of Leyendecker et al., discussed at the beginning of
this section, with those of Griffiths et al. In the former case, the insulating PMMA mask was shown to have strongly diminished
mixing, resulting in lower transport rates of the reacting ions, while in the latter case, buoyancy-driven transport rates into deep
high aspect ratio features higher than those expected from pure diffusion control were observed. Because Leyendecker et al. used a
redox couple to measure transport rates through microstructured electrodes, they were not able to benefit from potential
buoyancy-driven flows induced by the consumption of metal ions at the feature bottom.
Another series of studies focusing on feature scale uniformity in LIGA was carried out by Leith and Schwartz (1999a). Leith et al.
considered the electrodeposition of NiFe at 23 1C from sulfamate–chloride chemistries having various ratios of Ni to Fe electrolyte
loadings. They pointed out that the plating characteristics of an electrolyte must be carefully considered before employing it for
through-mask electrodeposition using thick resist. They found that electrolytes having less dissolved iron (e.g., 20:1 Ni2 þ :Fe2 þ as
opposed to 10:1 and 5:1 also considered in their study) are less sensitive to mixing variations at relatively high current densities,
suggesting that they would be more suitable for the electrodeposition of LIGA structures. Leith and Schwartz (1999b) also describe
a cell designed to maximize workpiece and pattern scale uniformity, using the NiFe system (as it is a challenging system for
uniformity) to demonstrate good uniformity across the wafer. The through thickness uniformity was not investigated in this study.
In another article, Wang et al. (2002) used an electrolyte with a 10:l Ni2 þ :Fe2 þ loading (where the deposited NiFe alloy
composition is more sensitive to mixing) to study convective–diffusion conditions during the through-mask deposition of LIGA
structures. They term the approach process archeology as the plated structure was planarized to half its deposited thickness for
compositional analysis via energy-dispersive X-ray analysis. By observing in plan view the planarized structures, regions in the
feature where locally high degrees of mixing occur could be easily identified as the Fe content as the alloy increases with mixing. In
this case, the authors were using the transport-sensitive deposition kinetics of the Fe as a type of tracer tool to study the mixing
within small cavities such as LIGA resist features. Another group of authors also considered the NiFe system to focus on the feature
scale uniformity of through-mask deposited LIGA structures. Thommes et al. used a sulfate-based NiFe electrolyte at 50 1C with a
Ni2 þ :Fe2 þ ratio of about 12:1 to deposit NiFe structures at 5 mA cm2 with good through-thickness uniformity. Figure 5,
reproduced from their data, shows the compositional behavior of the deposition system using a rotating disk electrode. It is clear
from Figure 5 that for low current densities the electrode rotation rate does not influence the deposited alloy composition,
suggesting that under these conditions the alloy composition is not greatly influenced by the amount of mixing. This relative
insensitivity to mixing would appear promising for the feature scale uniformity of LIGA NiFe structures.
The suitability of the authors’ deposition conditions for the electrodeposition of uniform high aspect ratio NiFe microstructures
is evidenced by the through-thickness compositional data shown in Figure 6. For a resist thickness of 180 mm and a feature
linewidth of 8 mm (aspect ratio 22.5), the authors obtain very good NiFe alloy uniformity throughout the entire structure thickness
Figure 5 Electrodeposited NiFE alloy composition dependence on deposition conditions, for conditions given by and replotted from Thommes
et al. (1994). The relative compositional insensitivity at low current densities suggests that the system may be a appropriate for the
electrodeposition of uniform, high aspect ratio structures. Reproduced from Thommes, A., Stark, W., Leyendecker, K., et al., 1994. LIGA
microstructures from a NiFe alloy: Preparation by electroforming and their magnetic properties. In: Romankiw, L.T., Herman Jr., D.A. (Eds.), Proc.
3rd Int. Symp. Magnetic Materials, Processes, and Devices PV, New Orleans, LA, pp. 94–96, with permission from the Electrochemical Society, Inc.
Author's personal copy
Electrodeposition 11
Figure 6 Electrodeposited NiFE alloy composition through-thickness uniformity replotted from Thommes et al. (1994). The structure width is
8 mm and its height is 180 mm. Open points are for deposition at 5 mA cm2, while the solid points are at 14 mA cm2. Deposition at the lower
current density (where composition was shown to be less sensitive to mixing) leads to uniform alloy content through the structure thickness, as
compared to 14 mA cm2. Reproduced from Thommes, A., Stark, W., Leyendecker, K., et al., 1994. LIGA microstructures from a NiFe alloy:
Preparation by electroforming and their magnetic properties. In: Romankiw, L.T., Herman Jr., D.A. (Eds.), Proc. 3rd Int. Symp. Magnetic Materials,
Processes, and Devices PV, New Orleans, LA, pp. 94–96, with permission from the Electrochemical Society, Inc.
using a deposition current density of 5 mA cm2. Through-thickness uniformity suffers at higher deposition current densities.
Figure 6 also shows experimental results for deposition at 14 mA cm2 using the same feature geometry. The Fe content increases
through the deposit as the top PMMA surface is approached, varying from about 20–50% across the thickness. Though not shown
here, the authors filled cylindrical features with a diameter of 5 mm and a height of 90 mm depositing NiFe at 5 mA cm2. They
show similarly good results as for the structure in Figure 6 deposited at the same current density. The electrodeposition process
outlined by Thommes et al. (1994) has been shown to be capable of producing high aspect ratio structures with good alloy
through-thickness compositional uniformity. To the authors’ knowledge, few other studies exist of alloy deposition through thick
resist where the feature scale uniformity is considered in such detail.
An aspect that is likely important in explaining the good results obtained by these authors is the bath temperature; Brenner has
discussed the fact that NiFe electrodeposition becomes less anomalous (and hence less transport sensitive) with increasing bath
temperature. Andricacos and Romankiw (1993) also discuss the importance of bath temperature as well as other process variables
on electrodeposited magnetic alloy composition. Given the limitations in obtaining good mixing in small LIGA features, it is not
surprising that achieving good feature scale uniformity for anomalous deposition systems (such as NiFe) is challenging for
geometries encountered in LIGA electrodeposition. New techniques are being employed for studying the electrodeposition
reaction inside of small features like those fabricated by the LIGA process; for example, special microelectrodes and chron-
oamperometric methods have been developed to measure the local metal cation concentrations during alloy electrodeposition
inside small cavities (Kuepper and Schultze, 1997). In the study mentioned previously, concentration variations inside of a cavity
where a NiCu alloy is being electrodeposited are investigated; they also observe the formation of a Ni hydroxide and nickel oxide
at the deposition surface during electrodeposition of the NiCu alloy from a sulfate electrolyte with potassium nitrate as supporting
electrolyte.
1.4.3 Summary: Uniformity at the workpiece, pattern, and feature scales in LIGA
The detailed study of Thommes et al. is a good example of the considerable effort required to develop an electrodeposition process
capable of producing uniform structures at the feature scale for geometries encountered in LIGA electrodeposition. When mixing
effects are important (as often the case in Ni alloy deposition), this is especially difficult. After some confidence in the feature scale
uniformity is attained for a given chemistry and set of deposition conditions, the uniformity at the pattern and workpiece scales
must still be addressed as well. This makes LIGA through-mask electrodeposition in some ways more challenging than electro-
deposition through thin resist, as the feature scale adds literally another dimension to the problem of obtaining uniformity across
multiple length scales. Considerable time and effort may be saved by first characterizing the electrodeposition kinetics and the
importance of mass transport for an electrodeposition process before attempting to apply it to LIGA fabrication (especially in the
case of an alloy system). If a good understanding of kinetics, transport, and alloy composition is in hand, electrolytes and
deposition parameters suitable for deposition through thick resist may be chosen more prudently.
Author's personal copy
12 Electrodeposition
Hsiharng Yang and Shung-Wen Kang (2000) addressed the difficulties associated in thickness non-uniformity in nickel
electroforming for the LIGA process. It happens like the edge thickness of plating area is usually twice or higher then center of
plating area. A secondary cathode (guard ring) was used to improve electroform uniformity and the same was reported to improve.
Cho et al. (2003) reported on prediction of reliability of LIGA Ni MEMS structure. Tensile specimen with dimension of
hundreds of micron were LIGA fabricated and were characterized in terms of their underlying microstructure, elevated tempera-
ture, tensile and creep strength, and their high cycle fatigue performance. The stiffness of these LIGA Ni structure was found to be
reduced by introduction of porosity during plating process and the strength of the structure was observed to decrease dramatically
at temperature above 200 1C.
Quandai Wang et al. (2009) reported on advancement of LIGA technology that rather than using thick resist technique the
microstructure with large structural height and high aspect ratio was obtained by multi level imprint through mask plating which
overcome synchrotron radiation accesible limitation in LIGA and unavoidable compromises’ in resolution, contrast, collimation,
and diffraction effect in UV LIGA process.
2 Properties of Electrodeposits
Ets2
6ð1 nÞtd R
where E and v are the Young’s modulus and Poisson ratio of the substrate, respectively, and the substrate is initially flat (Stoney,
1909).
Stress is a complicated function of all the plating parameters and is very much process dependent. For example, high-strength
alloys of nickel with manganese iron or cobalt are highly stressed in tensile. High-strength nickel produced from organic grain
refining agents is often stressed in compression. Varying the intrinsic stress through thickness has been used to intentionally induce
curvature in gold electroplated beams and flexures (Chinthakindi et al., 2002).
2.2 Adhesion
For many multilayer processes encountered in MEMS and semiconductor processing, adhesion of the metal deposit to the
substrate and pattern are critical to the success of the fabrication. Numerous forces can be applied to the metal interface that result
in failure, including the internal stress of the deposit itself, stresses generated as a result of the coefficient of thermal expansion
(CTE) mismatch during thermal processes, and stresses applied during the subsequent polishing of the metal such as that exerted
by chemical–mechanical polishing (CMP) in the copper Damascene process or by grinding of excess deposit in the LIGA process.
Metals that readily form a native oxide, such as aluminum, or that form a chemically resistant oxide, such as nickel, prove to be
difficult substrates for achieving good adhesion of electrodeposits. Standard methods are available and usually employ a series of
acid treatments followed by a strike layer or a thin layer of metal generated in a specially adapted electrolyte. The Woods Nickel
strike is such an example, consisting of 125 ml l1 of HCl and 240 g l1 of NiCl2 operated at 50 mA cm2 for a few minutes time
(Lowenheim, 1995).
While no universal method exists for determining an absolute value of adhesion, several methods are adequate for relative
evaluations. Methods include the peel test, shear test, ring shear test (Dini, 1993; Lowenheim, 1995). The measurement of peel
strength is readily adapted to thin films, but is highly dependent on strength and ductility of the metal film and requires large areas
Author's personal copy
Electrodeposition 13
(Klingenmaier and Dobrash, 1976). Other methods are purely qualitative, such as those to evaluate gold coatings: the coated
components are subjected to elevated temperatures and the presence of blisters indicates poor adhesion. Instruments that measure
the maximum shear force at failure provide a more quantitative measure of the adhesion. Thick-resist generated structures are
plated onto a coating or substrate and provided the failure occurs at the intended interface, the adhesion can be described. The
shortcoming of this approach is that the bulk strength of the substrate may be weaker than the interfacial strength, in which case
only a minimum strength can be assigned.
provided the resist is thick enough (a few hundred micrometers is needed for a conventional tester). This latter approach captures
the effects associated with feature scale transport, but suffers from long processing times and specialized lithography methods.
Some specialized instruments have been developed specifically for thin-film tensile testing, but the approaches are not standard.
2.4.2 Hardness
Another gage for the strength of an electrodeposited metal is its hardness, as determined by indenting a surface with a pyramidal
diamond tip. For many metals, an excellent correlation between the yield strength and the hardness can be achieved. For a given
load, the surface deforms plastically and the size of the remaining indentation is used to characterize the strength of the material.
The resulting hardness number has been correlated to the flow stress, or yield strength, for numerous metals, although the exact
relationship is unique for each material. A number of scales exist for the hardness, including Vickers, Knoop, Rockwell, and Brinell.
The Vickers hardness is defined as
P
H ¼ 1854
a2
where a is the length of the indent diagonal in microns and P is the load in grams-force. For thin films and coatings, a
microhardness test is commonly used, where the applied load is small enough to reduce the indent size far below the thickness of
the deposit. So for a 500 VHN25 nickel electrodeposit and a 25-g load, the indent diagonal is 9.6 mm, setting the minimum feature
size for measurement around 40 mm. A requirement for the microhardness test is that the penetration depth is less than a third
of the total depth of the material; otherwise, the substrate will influence the measurement. Furthermore, the surface being
indented must be optically flat to provide an accurate measurement. The granularity of as-deposited films makes taking a reliable
measurement without polishing difficult. As a result, samples must be carefully prepared to provide rigid backing, depth of
material, and a smooth surface. Nevertheless, the technique is straightforward and commonly used to characterize
electrodeposited metals.
2Pw2
s¼
ht
where the stress is related to the pressure P, the width of the membrane w, the center deflection h, and the film thickness t (Xiang
et al., 2002). And,
h2
e ¼ e0 þ
6w2
s ¼ s0 þ Kd1=2
where s can be the flow stress or microhardness and d is the grain diameter. Li and Ebrahimi (2003) have examined the Hall–Petch
relation for a number of nanocrystalline nickel and nickel alloy electrodeposits.
Author's personal copy
Electrodeposition 15
Figure 7 Example of nickel-plated microelectromechanical systems (MEMS) cantilever for use as an electrical test probe. Reprinted from K.,
Kawamura, S., Itoh, T., et al., 2003. Electroplating Ni micro-cantilevers for low contact-force IC probing. Sensor. Actuator. A 103, 116–121, with
permission from Elsevier.
Some amount of chloride is present to assist dissolution of the nickel anode, but specially formulated nickel anodes possessing
sulfur will sufficiently release nickel without the chloride. Table 2 lists a common formulation for a sulfamate electrolyte, which is
used for high-speed electroforming owing to the reduced stress and slightly higher concentrations of nickel available. Typically, a
concentrate of nickel as nickel sulfamate (24 oz gal1 or 180 g l1), available from a number of commercial vendors, is diluted to
the desired concentration.
Table 3 lists a representative formulation for a Watts nickel electrolyte with saccharin as an organic brightner to reduce stress
and refine the grain size. Sulfamate electrolytes can be used in conjunction with these additives as well, and the resulting deposits
are lustrous, smooth, low stresses, and high strength. The downside to these addition agents, as mentioned previously, is the
incorporation of sulfur into the nickel deposit.
A range of temperatures is feasible for nickel electroplating, but usually falls within 32–60 1C. The low end of the temperature
range is dictated by the boric acid, a critical component to both types of electrolytes. Boric acid, in the range 30–40 g l1, is
believed to act as a buffer to mitigate the local rise in pH associated with hydrogen formation. The amount of boric acid is close to
the solubility limit, and temperatures below 32 1C should be employed with caution. A wetting agent or surfactant such as sodium
lauryl sulfate is also desirable to inhibit pitting that can result when hydrogen clings to the growing surface. A low surface tension,
which can also be accomplished with higher temperatures, is especially critical for plating in patterned resists where feature walls
can pin bubbles within the feature.
While nickel sulfamate-derived electrodeposits are stronger than most other metals and easily integrated due to low stresses,
some applications require a thermally stable alloy with high strength and resistance to embrittlement. The trade-off is that these
Author's personal copy
Electrodeposition 17
alloys (Ni–Fe, Ni–Co, and Ni–Mn) are highly stressed as-deposited with more complicated processes. An extensive literature exists
for the electrodeposition of magnetic Ni–Fe and Ni–Co alloys, so the processes are only briefly described here. Table 4 provides the
electrolyte used in Leith and Schwartz (1999a) as an example of Ni–Fe deposition in high aspect ratio structures. The high stresses
encountered required the saccharin stress-reducing additive, rendering the deposit susceptible to embrittlement. Furthermore, the
alloy composition was sensitive to the extent of mass transfer, a difficulty for Ni–Fe and Ni–Co alloys.
A high-strength nickel alloy developed to avoid these issues with mass transport and electrolyte sensitivity is Ni–Mn, where the
Mn content is low, less than 1% (Kelly et al., 2003). Uniform alloy content through the thickness of high aspect ratio molds
demonstrates the reduced sensitivity to mass transport with respect to the codepositing element. The electrolyte is based on
sulfamate and pulse plating is used to alleviate some of the tensile stress. The low temperatures employed dictate caution with
extended use of the electrolyte (Goods et al., 2006; Table 5).
3.3 Gold
Gold finds use as both a corrosion-resistant coating and an electrical conductor. Through-resist plating of gold has been extensively
used in microelectronics, particularly for packaging. Lithographically patterned gold also finds use in the fabrication of X-ray masks
for the LIGA process.
Author's personal copy
18 Electrodeposition
Temperature (1C) 25
J (mA cm2) 10
Anode Cu or
Cu–P
Early electrolytes were based on cyanide complexes (Green et al., 2003; Morrissey, 1993) of the gold, which were generally
incompatible with photoresists. Formulations common to microelectronics and MEMS consist of sulfite-based chemistries
(Horkans and Romankiw, 1977). Table 7 gives a representative formulation based on Green et al.
Electrodeposition is also the key to the synthesis of many of the nanostructured thermoelectric materials. By using the template
synthesis method in nanoporous alumina, nanowires of thermoelectric materials are electrodeposited and the properties improved
over bulk materials (Borca-Tasciuc et al., 2004). A clever integration of such a nanostructured thermoelectric material into a MEMS
device has been demonstrated (Wang et al., 2005). The promise for improved materials and novel applications promise to make
this an important contribution to MEMS by electrodeposition.
Meier et al. (2015) reported the formation of copper and nickel nanowire by electrodeposition technique inside alumina
template. In order to expose deposited membrane, the sample was immersed in solution of sodium hydroxide to dissolve alumina
membrane and to expose generated deposit.
Author's personal copy
Electrodeposition 19
Antenucci et al. (2015) reported electrodeposition of graphene on open cell aluminum foams. The experimental findings
unarcaned that manufactured metal foam possesses higher mechanical resistance and thermal conductivity and low
processing costs.
Devivier et al. (2015) reported application of electrodeposition technique to deposit nickel for exalting mechanical properties
of open cell aluminum foam and strain was measured using optical extensometer. The results proved increase of maximum stress
and increase in resistance to corrosion which allows it to use in aggressive environment.
4 Conclusion
The chapter presented a detailed overview of electrodeposition process. The process is versatile and was used to deposit variety of
material and also at nano level. The process proved advantageous on grounds to improve wear resistance, corrosion protection and
esthetics value. But concerning uniformity of the coating it ends up as lumpy and uneven which calls for further processing
operation. Another important concern of this process is the choice of coating. If coating is too brittle, it will crack and that crack
may not be apparently visible to naked eyes but impurities could lead to overall destruction of electroplated layer. Nevertheless a
robust manufacturing process free off any limitations is still to transform from conception to reality. Efforts may be taken on the
ways to mend a selected issue and by and by the whole process will be flawless.
References
Amaya, R.E., Levenets, V., Tarr, N.G., Plett, C., 2004. Copper coplanar waveguides in Si substrates for 10 GHz applications. J. Vac. Sci. Technol. A 22, 847–850.
Amblard, J., Epelboin, I., Froment, M., Maurin, G., 1979. Inhibition and nickel electrocrystallization. J. Appl. Electrochem. 9, 233–242.
Andricacos, P.C., Romankiw, L.T., 1993. Magnetically soft materials in data storage: Their properties and electrochemistry. In: Gerischer, H., Tobias, C.W. (Eds.), Advances in
Electrochemical Science and Engineering. Weinheim: VCH Verlagsgesellschaft.
Antenucci Guarino, A., Tagliaferri, V., Ucciardello, N., 2015. Electro-deposition of graphene on aluminium open cell metal foams. Mater. Design 71, 78–84.
Atanassov, N., Schils, H.W., 1999. Influence of structural parameters on the properties of electrolytic Ni–Mn–S deposits. J. Appl. Electrochem. 29, 51–57.
Bard, A.J., Faulkner, L., 2001. Electrochemical Methods and Fundamentals and Applications. New York, NY: John Wiley and Sons.
Borca-Tasciuc, D.A., Chen, G., Prieto, A., et al., 2004. Thermal properties of electrodeposited bismuth telluride nanowires embedded in amorphous alumina. Appl. Phys. Lett.
85, 6001–6003.
Bottner, H., 2005. Micropelt miniaturized thermoelectric devices: Small size, high cooling power densities, short response time. In: 24th Int. Conf. Thermoelectric (ICT),
Clemson, SC, USA, June 19–23, 2005. IEEE Clemson, SC, pp. 1–8.
Bottner, J., Nurnus, A., Gavrikov, G., et al., 2004. New thermoelectric components using microsystem technologies. J. Microelectromech. Syst. 13, 414–420.
Brenner, A., 1963. Electrodeposition of Alloys. New York, NY: Academic Press.
Chinthakindi, A.K., Bhusari, D., Dusch, B.P., et al., 2002. Electrostatic actuators with intrinsic stress gradient. I. Materials and structures. J. Electrochem. Soc. 149, H139–H145.
Cho, H.S., Hemker, K.J., Lian, K., Goettert, J., Dirras, G., 2003. Measured mechanical properties of LIGA Ni structures. Sensor. Actuator. A 103, 59–63.
Choi, P., Al-Kassab, T., Gartner, F., Kreye, H., Kirchheim, R., 2003. Thermal stability of nanocrystalline nickel-18 at.% tungsten alloy investigated with the tomographic atom
probe. Mater. Sci. Eng. A353, 74–79.
Choi, Y.-S., Yoon, J.-B., 2004. Experimental analysis of the effect of metal thickness on the quality factor in integrated spiral inductors for RF ICs. IEEE Electr. Device Lett. 25,
76–79.
Czerwinksi, F., Szpunar, J.A., 2000. Texture instability in Ni electrodeposits applied in optical disk technology. J. Mater. Sci. 35, 331–335.
Da Silva, L.W., Kaviany, M., 2005. Fabrication and measured performance of a first-generation microthermoelectric cooler. J. Microelectromech. Syst. 14, 1110–1117.
Datta, M., Landolt, D., 2000. Fundamental aspects and applications of electrochemical microfabrication. Electrochim. Acta 45, 2535–2558.
DeBecker, B., West, A.C., 1996. Workpiece, pattern, and feature scale current distributions. J. Electrochem. Soc. 143, 486–492.
Devivier, C., Tagliaferri, V., Trovalusci, N.F., Ucciardello, N., 2015. Mechanical characterization of open cell aluminum foams reinforced by nickel electro-deposition. Mater.
Design 86, 272–278.
Dini, J.W., 1993. Electrodeposition: The Materials Science of Coatings and Substrates. Norwich, NY: Noyes Publication.
Drese, K.S., 2004. Design rules for electroforming in the LIGA process. J. Electrochem. Soc. 151, D39–D45.
Dukovic, J.O., 1994. Current distribution and shape change in electrodeposition of thin films for microelectronic fabrication. In: Gerischer, H., Tobias, C.W. (Eds.), Advances in
Electrochemical Science and Engineering. Weinheim: VCH.
Goods, S.H., Kelly, J.J., Talin, A.A., Michael, J.R., Watson, R.M., 2006. Electrodeposition of Ni from low-temperature sulfamate electrolytes. J. Electrochem. Soc. 153,
C318–C324.
Goods, S.H., Kelly, J.J., Yang, N.Y.C., 2004. Electrodeposited nickel–manganese: An alloy for microsystem applications. Microsyst. Technol. 10, 498–505.
Green, T.A., Liew, M.-J., Roy, S., 2003. Electrodeposition of gold from a thiosulfate–sulfite bath for microelectronic applications. J. Electrochem. Soc. 150, C104–C110.
Griffiths, S.K., Crowell, J.A.W., Kistler, B.L., Dryden, A.S., 2004. Dimensional errors in LIGA-produced metal structures due to thermal expansion and swelling of PMMA.
J. Micromech. Microeng. 14, 1548.
Griffiths, S.K., Losey, M.W., Hachman, J.T., et al., 2005. Resist substrate studies for LIGA microfabrication with application to a new anodized aluminum substrate.
J. Micromech. Microeng. 15, 1700–1712.
Griffiths, S.K., Nilson, R.H., Bradshaw, R.W., et al., 1998. Transport limitations in electrodeposition for LIGA microdevice fabrication. Proc. SPIE 3511, 364–375.
Guckel, H., 1993. Formation of Microstructures by Multiple Level Deep X-ray Lithography with Sacrificial Metal Layers. Madison, WI: Wisconsin Alumni Research Foundation.
Harper, J.M., Cabral Jr., C., Andricacos, P.C., et al., 1999. Mechanisms for microstructure evolution in electroplated copper thin films near room temperature. J. Appl. Phys.
86, 2516–2525.
Hayashi, K., Fukui, K., Tanaka, Z., Kondo, K., 2001. Shape evolution of electrodeposited bumps into deep cavities. J. Electrochem. Soc. 148, C145–C148.
Horkans, J., Romankiw, L.T., 1977. Pulsed potentiostatic deposition of gold from solutions of the Au(I) sulfite complex. J. Electrochem. Soc. 124, 1499–1505.
Hsiharng Yang, Shung-Wen Kang, 2000. Improvement of thickness uniformity in nickel electroforming for the LIGA Process. Int. J. Mach. Tools Manu. 40, 1065–1072.
Itoh, T., Kawamura, S., Kataoka, K., Suga, T., 2003. Contact properties of micromachined Ni probes. In: Proccedings of the 49th IEEE Holm Conference on Electrical Contacts,
Washington, DC, USA.
Author's personal copy
20 Electrodeposition
Jordan, M., 2000. Electrodeposition of tin–lead alloys. In: Paunovic, M. (Ed.), Modern Electrodeposition, fourth ed. New York, NY: John Wiley and Sons.
Kataoka, K., Kawamura, S., Itoh, T., et al., 2003. Electroplating Ni micro-cantilevers for low contact-force IC probing. Sensor. Actuator. A 103, 116–121.
Keller, R.M., Baker, S.P., Arzt, E., 1999. Stress–temperature behavior of unpassivated thin copper films. Acta Mater. 47, 415–426.
Kelly, J.J., Goods, S.H., Yang, N.Y.C., 2003. High performance nanostructured Ni–Mn alloy for microsystem applications. Electrochem. Solid State Lett. 6, C88–C91.
Kim, B., Ritzdorf, T., 2003. Electrodeposition of near eutectic SnAg solders for wafer level packaging. J. Electrochem. Soc. 150, C577–C584.
Kim, B.-H., Kim, H.-C., Chun, K., Ki, J., Tak, Y., 2004. Cantilever-type microelectromechanical systems probe card with through-wafer interconnects for fine pitch and high-
speed testing. Jpn. J. Appl. Phys. 43, 3877–3881.
Klingenmaier, O.J., Dobrash, S.M., 1976. Peel test for determining the adhesion of electrodeposits on metallic substrates. In: Mittal, K.L. (Ed.), Adhesion Measurement of Thin
Films, Thick Films and Bulk Coatings. Philadelphia, PA: ASTM.
Kondo, K., Fukui, K., Uno, K., Shinohara, K., 1996. Shape evolution of electrodeposited copper bumps. J. Electrochem. Soc. 143, 1880–1886.
Kuepper, M., Schultze, J.W., 1997. Spatially resolved concentration measurements during cathodic alloy deposition in microstructures. Electrochim. Acta 42, 3023–3031.
Landolt, D., 1994. Electrochemical and materials science aspects of alloy deposition. Electrochim. Acta 39, 1075–1090.
Lee, S., Kwon, T.H., 2006. Mass-producible replication of highly hydrophobic surfaces from plant leaves. Nanotechnology 17, 3189–3196.
Leith, S.D., Schwartz, D., 1999a. High-rate through-mold electrodeposition of thick (200 m) NIFE MEMS components with uniform composition. J. Microelectromech. Syst. 8,
384–392.
Leith, S.D., Schwartz, D.T., 1999b. Through-mold electrodeposition using the uniform injection cell (UIC): Workpiece and pattern scale uniformity. Electrochim. Acta 44,
4017–4027.
Leyendecker, K., Bacher, W., Stark, W., Thommes, A., 1994. New microelectrodes for the investigation of the electroforming of LIGA microstructures. Electrochim. Acta 39,
1139–1143.
Li, H.Q., Ebrahimi, F., 2003. An investigation of thermal stability and microhardness of electrodeposited nanocrystalline nickel–21% iron alloys. Acta Mater. 51, 3905–3913.
Lowenheim, F.A., 1995. Electroplating. Bristol: Technical Reference Publications.
Lu, L., Shen, Y., Chen, X., Qian, L., Lu, K., 2004. Ultrahigh strength and high electrical conductivity in copper. Science 304, 422–426.
Magri, P., Boulanger, C., Lecuire, J.M., 1996. Synthesis, properties and performances of electrodeposited bismuth telluride films. J Mater. Chem. 6, 773–779.
Malek, C.K., Saile, V., 2004. Applications of LIGA technology to precision manufacturing of high-aspect-ratio micro-components and -systems: A review. Microelectron. J. 35,
131–143.
Marti, J.L., Lanza, G.P., 1969. Hardness of sulfamate nickel deposits. Plating 56, 377–385.
Martin-Gonzalez, M.S., Prieto, A.L., Gronsky, R., Sands, T., Stacy, A.M., 2002. Insights into the electrodeposition of Bi2Te3. J. Electrochem. Soc. 149, C546–C554.
Massoud-Ansari, S., Mangat, P.S., Klein, J., Guckel, H., 1996. A multi-level, LIGA-like process for three dimensional actuators. In: The 9th Annual International Workshop on
Micro Electro Mechanical Systems, 1996, MEMS ’96, Proceedings. An Investigation of Micro Structures, Sensors, Actuators, Machines and Systems. IEEE, San Diego, CA,
USA.
Mehdizadeh, S., Dukovic, J., Andricacos, P.C., Romankiw, L.T., Cheh, H.Y., 1990. Optimization of electrodeposit uniformity by the use of auxiliary electrodes. J. Electrochem.
Soc. 137, 110–117.
Mehdizadeh, S., Dukovic, J., Andricacos, P.C., Romankiw, L.T., Cheh, H.Y., 1992. The influence of lithographic patterning on current distribution: A model for microfabrication
by electrodeposition. J. Electrochem. Soc. 139, 78–91.
Mehdizadeh, S., Dukovic, J., Andricacos, P.C., Romankiw, L.T., Cheh, H.Y., 1993. The influence of lithographic patterning on current distribution in electrodeposition:
Experimental study and mass-transfer effects. J. Electrochem. Soc. 140, 3497–3505.
Meier, L.A., Alvarez, A.E., Garcia, S.G., del Barrio, M.C., 2015. Formation of Cu and Ni Nanowires by electrodeposition. Procedia Mater. Sci. 8, 617–6622.
Morrissey, R., 1993. A versatile non-cyanide gold plating system. Plat. Surf. Finish. 80 (4), 75–79.
Nielsch, K., Muller, F., Li, A.P., Gosele, U., 2000. Uniform nickel deposition into ordered alumina pores by pulsed electrodeposition. Adv. Mater. 12, 582–586.
Nilson, R.H., Griffiths, S.K., 2003. Natural convection in trenches of high aspect ratio. J. Electrochem. Soc. 150, C401–C412.
Park, K.Y., Park, J.Y., Lee, J.C., et al., 2000. A new micromachined bandpass filter on a quartz substrate. Jpn. J. Appl. Phys. 39 (6B), 638–640.
Park, S., Schift, H., Padeste, C., et al., 2004. Anti-adhesive layers on nickel stamps for nanoimprint lithography. Microelectron. Eng. 73–74, 196–201.
Perez-Prado, M.T., Vlassak, J.J., 2002. Microstructural evolution in electroplated Cu thin films. Scripta Mater. 47, 817–823.
Puippe, J.C., Leaman, F., 1986. Theory and Practice of Pulse Plating. Orlando, FL: American Electroplaters and Surface Finishers Society.
Quandai Wang, Yugang Duan, Yucheng Ding, et al., 2009. Investigation of LIGA like process based on multilevel imprint lithography. Microelectr. J. 40, 149–155.
Rajput, M.S., Pandey, P.M., Jha, S., 2015. Modelling of high speed selective Jet electrodeposition process. J. Manuf. Process. 17, 98–107.
Safranek, W.H., 1986. The Properties of Electrodeposited Metals and Alloys. Orlando, FL: American Electroplaters and Surface Finishers Society.
Schlesinger, M., Paunovic, M., 2000. Modern Electroplating. New York, NY: John Wiley and Sons.
Slavcheva, E., Mokwa, W., Schnakenberg, U., 2005. Electrodeposition and properties of NiW films for MEMS application. Electrochim. Acta 50, 5573–5580.
Snyder, G.J., Lim, J.R., Huang, C.K., Fleurial, J.P., 2003. Thermoelectric microdevice fabricated by a MEMS-like electrochemical process. Nat. Mater. 2, 528–531.
Stoney, G.G., 1909. The tension of metallic films deposited by electrolysis. Proc. R. Soc. Lond. 82, 172–175.
Takahashi, M., Katou, Y., Nagata, K., Furuta, S., 1994. The composition and conductivity of electrodeposited Bi–Te alloy films. Thin Solid Films 240, 70–72.
Talin, A.A., Marquis, E.A., Goods, S.H., Kelly, J.J., Miller, M.K., 2006. Thermal stability of Ni–Mn electrodeposits. Acta Mater. 54, 1935–1947.
Thommes, A., Stark, W., Leyendecker, K., et al., 1994. LIGA microstructures from a NiFe alloy: Preparation by electroforming and their magnetic properties. In: Romankiw, L.T.,
Herman Jr., D.A. (Eds.), Proc. 3rd Int. Symp. Magnetic Materials, Processes, and Devices PV, New Orleans, LA, pp. 94–96.
Thuvander, M., Abraham, M., Cerezo, A., Smith, G.D.W., 2001. Thermal stability of electrodeposited nanocrystalline nickel and iron–nickel alloys. Mater. Sci. Technol. 17,
961–970.
Tittes, K., Bund, A., Plieth, W., et al., 2003. Electrochemical deposition of Bi2Te3 for thermoelectric microdevices. J. Solid State Electrochem. 7, 714–723.
Wang, W., Jia, F., Huang, Q., Zhang, J., 2005. A new type of low power thermoelectric micro-generator fabricated by nanowire array thermoelectric material. Microelectron. Eng.
77, 223–229.
Wang, W., Leith, S.D., Schwartz, D.T., 2002. Convective–diffusive mass transfer inside complex micro-molds during electrodeposition. J. Microelectromech. Syst. 11 (2),
118–124.
Watanabe, H., Hayashi, S., Honma, H., 1999. Microbump formation by noncyanide gold electroplating. J. Electrochem. Soc. 146, 574–579.
Wu, Q., Fu, J., Gu, X., Shi, H., Lee, J., 2003. MEMS-based transmission lines for microwave applications. In: Chiao, J.C., Varadan, V.K., Cané, C. (Eds.), Smart Sensors,
Actuators, and MEMS, Proceedings of the SPIE, Maspalomas, Gran Canaria, Spain.
Xiang, Y., Chen, X., Vlassak, J.J., 2002. The mechanical properties of electroplated Cu thin films measured by means of the bulge test technique. In: Ozkan, C.S., et al. (Eds.),
Thin Films: Stresses and Mechanical Properties IX, pp. 189–195 (Mater. Res. Soc. Sym. Proc. 695, Warrendale, PA, 2002).