Journal of Alloys and Compounds 483 (2009) 321333

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

Concepts for the design of advanced nanoscale PVD multilayer protective

thin lms
M. Stueber , H. Holleck, H. Leiste, K. Seemann, S. Ulrich, C. Ziebert
Forschungszentrum Karlsruhe, Institute for Materials Research I (IMF-I), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany

a r t i c l e

i n f o

Article history:
Received 30 August 2007
Received in revised form 21 July 2008
Accepted 29 August 2008
Available online 17 November 2008
Keywords:
Thin lms
Surfaces and interfaces
Vapour deposition
Microstructure

a b s t r a c t
Technological challenges in future surface engineering applications demand continuously new material
solutions offering superior properties and performance. Concepts for the design of such advanced multifunctional materials can be systematically evolved and veried by means of physical vapour deposition.
The classical multilayer coating concept today is well established and widely used for the design of protective thin lms for wear and tribological applications. It has proven great potential for the development of
novel thin lm materials with tailored properties. In the past decade, the emerging new class of nanoscale
coatings has offered to the material scientists an even more powerful toolbox for the engineering thin lm
design through a combination of the multilayer concept with new nano-coatings. Some examples are the
use and integration of low friction carbon-based nanocomposites in advanced multilayer structures or
the stabilization of a specic coating in another structure in a nanolaminated multilayer composite. This
paper reviews the latest developments in hard, wear-resistant thin lms based on the multilayer coating concept. It describes the integration of nanocrystalline, amorphous and nanocrystalline/amorphous
composite materials in multilayers and covers various phenomena such as the superlattice effect, stabilization of materials in another, foreign structure, and effects related to coherent and epitaxial growth.
Innovative concepts for future, smart multilayer designs based on an extremely ne structural ordering
at the nanoscale are presented as well.
2008 Elsevier B.V. All rights reserved.

1. Multilayer coatings for wear protection: pioneering work

and fundamental knowledge
The realization of future technical solutions for tribology-related
engineering applications in the tool industry and highly-stressed
components for instance in the automotive or aircraft industries
requires the development of new multifunctional thin lm materials that meet the challenges of providing superior mechanical,
tribological, chemical and high-temperature properties and performance. Concepts for the design of such advanced coatings can
be systematically evolved and veried by means of physical vapour
deposition (PVD). The classical multilayer coating concept today
is well established and widely used for the design of protective
thin lms for wear and tribological applications. It has proven
great potential for the development of novel thin lm materials
with tailored properties. In the past decade, the emerging new
class of nano-coatings has offered to the material scientists an
even more powerful toolbox for the engineering thin lm design

Corresponding author. Tel.: +49 7247 82 3889; fax: +49 7247 82 4567.
E-mail address: michael.stueber@imf.fzk.de (M. Stueber).
0925-8388/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2008.08.133

through a combination of the multilayer concept and new coatings

with extremely ne structural ordering at the nanoscale leading to
signicantly enhanced properties and functionalities.
This paper presents recent developments in hard, wear-resistant
thin lms based on the multilayer coating concept. It briey
addresses the pioneering work on multilayers and focuses on a
description of the state-of-the-art in multilayer thin lms based on
nanoscale approaches. Innovative concepts for future, smart multilayer designs based on an extremely ne structural ordering at
the nanoscale are discussed as well. The paper is limited to multilayers composed of hard materials with metallic and/or covalent
bonding characteristics only and does not refer to multilayers with
metal layers or composed of alternating metal and ceramic hard
layers. Excellent reviews on various aspects of multilayer thin lm
development are available [114].
Since the rst reports on the deposition of hard and even superhard multilayer thin lms and their corresponding microstructure
formation mechanisms such as superlattice growth came up after
the mid 1980s [1520], an enormous run on both experimentally
and theoretically driven research on the development of tailormade multilayer coatings was initiated. (Please note: Timely parallel
developments on metal/metal multilayer coatings and the so-called
supermodulus effect are not referred to here; for an introduction

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M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

Fig. 1. Change in properties of nanoscale multilayer coatings as a function of the

interface volume (schematically, disregarding superlattice structures), re-designed
from a review article of Holleck [8].

into this topic see for example the early papers of Schuller and
co-workers [21,22], Wolf and Lutsko [23], or the review articles
of Barnett and Shinn [4] and of Abadias et al. [14] and references
therein.) Based on early results obtained for classical multilayer
coatings, which in the easiest model can be described as an alternating layer-by-layer arrangement of two single-phase materials
with remarkable individual layer thickness (in the range of some
ten or hundred nanometers), it was soon recognized, that a signicant reduction both of the thickness of the individual layers and of
the crystallite sizes of the layer materials (down to a few nanometers) can result in a drastic enhancement of the thin lm properties.
Besides the properties of the individual layer materials, the grain
boundaries and interfaces play an important role for the overall
coating properties with regard to the nanoscale architecture of the
coatings. Fig. 1, re-designed from a review article of Holleck [8],
displays some general conclusions on the structureproperty relationships of hard PVD multilayer coatings composed of single layer
materials with similar bonding characteristics (disregarding compositionally modulated superlattice structures). The properties and
performance of such coatings were found to vary systematically
with the amount and area of interfaces (denoted as interface vol-

ume in [8], taking into account that interfaces mostly are extended
over a few nm). It was demonstrated that optimum properties and
performance could be achieved at specic values of the interface
volume. Not all properties reached their optimum levels at the
same interface volume or at the same number of layers. For specic multilayer lms, in example combinations of TiN, TiC, and
TiB2 , a range has been identied where optimum properties could
be achieved: this range included some 100200 layers for a 5 m
thick coating. Considering the bilayer modulation period , introduced as a characteristic of superlattice coatings (see Section 2),
optimum properties were obtained for such coatings for values
of  between 50 and 100 nm. Holleck classied multilayer coatings by the type, bonding and microstructural characteristics of the
individual layer materials as well as by the specic nano-design
achieved by interface modeling [8], a systematic described in more
detail in [24]. Many of the design concepts for multilayer thin
lms realized perfectly later on by other research groups were
anticipated by his early, trendsetting papers [1,25]. With regard
to the covalent bonding characteristics of most nitrides, carbides
and borides used in multilayer coatings, Holleck suggested to seriously consider strengthening and toughening mechanisms known
for brittle bulk ceramics when discussing mechanical, elastic and
plastic properties of multilayers [5]. These include crack initiation, crack propagation and crack energy dissipation, for example
by crack deection. When a multilayer surface is exposed to a
mechanical load, various effects may play together, covering surface
effects (crack initiation), in-layer, interface, phase or grain boundary and through-coating effects. A crack starting from the coating
surface may be split and deected at the grain or phase boundaries within a layer (grain boundary toughening or hardening) or
at the interface zone between the layers (interface toughening or
hardening). On the other hand, local delamination can occur at
interfaces through the opening of nano-voids which can result in
local stress relaxation and even plasticity at the nanoscale. Furthermore, there should be an interaction of cracks with periodic
strainstress elds across the interfaces in nanoscale multilayers,
and also an interaction of through going cracks with the substrate material. These mechanisms are shown schematically in
Fig. 2. Obviously, internal interfaces can have a benecial effect

Fig. 2. Toughening and strengthening mechanisms in ceramic multilayer coatings (schematically) according to Holleck and Schier [5].

M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

on the microscopic and macroscopic coating properties when their

amount is carefully adjusted to the overall volume of the coating.
The modeling and understanding of elastic and plastic properties of
multilayers is however more complex as many coatings also display
large amounts of metal bonds and grow in metal-like lattice structures. Hence, dislocation motion and interaction of dislocations
with microstructural features such as grain boundaries, interfaces
and column boundaries in PVD coatings as well as various defects
and coherency strains between the individual layers have to be
considered as well [9].
Further progress in multilayer thin lm research was stimulated
by the rst successful epitaxial stabilization of a layer material
in a different microstructure as shown by Setoyama et al. [26]
and Madan et al. [27] for the TiNAlN system (see Section 3). The
increasing knowledge on existing PVD methods and emerging new
deposition technologies supported the development of multilayer
coatings as well [2,28]. Considering the period from the mid 1990s
until today, a large variety of highly sophisticated nanoscale multilayer coatings with promising properties has been developed,
however only a few coatings have been introduced already into
the market in engineering applications. In fact, there is a contrast between very tricky multilayer growth processes available in
the laboratories and the demand for easy to scale-up deposition
processes for industrial use [11]. On the other hand, a fairly undeveloped database of detailed experimental information on various
types of wear-resistant, hard multilayer coatings (covering nearly
all combinations of nitrides, carbides, carbonitrides, oxides and
other hard phases such as boron carbide, boron nitride or diamondlike carbon) has been collected until today, which should give rise
to the expectation of similar breakthroughs through new coating
materials in the future as was related to the rst reports on hard
multilayers some decades ago.
To provide a complete overview of this eld of materials science
is almost impossible. Thus only a few, but important highlights
of the state-of-the-art in multilayer development with the focus
on principal design concepts are described in this paper. This
review is exemplarily amended by selected results obtained by
the authors. According to Yashar and Sproul [7] multilayer coatings can be classied in two categories: iso-structural (individual
layers have the same structure) and non-iso-structural (individual layers have different structures). With regard to the increasing
number of publications dealing with new types of multilayer
coatings (integration of amorphous layer materials or of novel multiphase, nanocrystalline/amorphous composite materials, or even
completely amorphous multilayer systems), both the classications
of Yashar and Sproul and of Holleck [7,8] today might be updated
to cover all these different materials. Multilayer design by epitaxial stabilization and superlattice structure formation has become a
major driver in coating development today and are therefore used
as a main characteristic to classify the coatings. Section 2 describes
multilayer coatings without epitaxial stabilization effects, while in
Section 3 multilayer coatings using epitaxial stabilization effects
are presented. Selected new concepts for multilayer design with
ne-scale structural ordering are suggested in Section 4.

323

more or less, and dependent on the growth conditions, with a polycrystalline, columnar or nanocolumnar structure according to the
Thornton model [29], while under certain conditions the growth of
single-crystalline coatings is possible. A signicant part of the work
done so far on hard PVD multilayer coatings can be attributed to
the combination of such materials. One should note, that the same
multilayer material system can exist in different structures showing different properties, which depends on the material selection,
the deposition processes and kinetics of growth, and on the special nanoscale thin lm architecture (i.e. one may design the same
multilayer coating in the form of a superlattice showing signicant hardness enhancement or as a nanoscale multilayer coating
without superlattice structure and properties). In this paper, a more
phenomenological description of growth effects in multilayer coatings is provided, while a materials science based consideration is
under preparation.
2.1. Single-crystalline superlattice thin lms
Numerous papers are available today on multilayers composed
of two nitride or carbide hard materials with cubic face-centered
structure and metallic bonding character (i.e. TiN, VN, ZrN, CrN,
NbN, TiC, and VC). The periodic arrangement of such materials
in a nanoscale multilayer structure can result in the growth of a
perfect compositionally modulated structure. A breakthrough in
the development of superhard coatings was achieved in 1987 by
Helmersson et al. [16], who demonstrated an enormous increase
of the hardness of single-crystalline TiN/VN multilayers epitaxially
grown on MgO substrates by reactive magnetron sputtering at substrate temperature of 750 C (Fig. 3). The hardness enhancement
occurred at a bilayer modulation period  of 5.2 nm, and maximum hardness values of 5560 kg/mm2 were determined (while the
hardness for pure single-crystal TiN and VN lms were 2200 and
1620 kg/mm2 , respectively). This effect since then was referred to as
superlattice effect, and the corresponding structure as superlattice
structure. Superlattice structures with superlattice effect (significant hardness enhancement) were observed for various other
single-crystalline nitride multilayer coatings as well: Mirkarimi et

2. Nanoscale multilayer coatings without epitaxial

stabilization effects
The transition metal nitrides, carbides and carbonitrides (especially those of the elements of the groups IV B, V B, and, VI B of the
periodical system) belong to the most relevant coating materials
for wear applications. The majority of these nanocrystalline hard
PVD coatings are usually synthesized by various magnetron sputtering or arc evaporation processes (or hybrid deposition processes
combining sputtering and arc methods). All these coatings grow

Fig. 3. Microindentation hardness of TiN/VN superlattice structure as a function of

the superlattice period. Diagram originally presented by Helmersson et al. [16].

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M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

al. [19] reported enhanced hardness in TiN/V0.6 Nb0.4 N superlattices

grown by reactive magnetron sputtering on MgO substrates at a
substrate temperature of 700 C; the materials for the multilayer
design were selected carefully by providing layer materials showing no lattice mismatch. Further systematic studies of Mirkarimi
et al. [30] addressed the impact of lattice mismatch and coherency
strains at layer interfaces on possible hardness changes. Shinn et
al. also reported signicant hardness enhancements for TiN/NbN
superlattices [31] (deposited at temperatures around 700 C on
MgO substrates again). A more detailed insight into this eld of
multilayer development is given by the review articles of Barnett
and Shinn [4], Yashar and Sproul [7], and Hultman [13].
2.2. Poly-crystalline superlattice thin lms with superlattice effect
The above-described basic experiments on the epitaxial growth
of superlattice structures on single-crystalline substrates at elevated temperatures were useful for the identication of general
hardening mechanisms. Using however different substrate materials (i.e. poly-crystalline ones) or applying less severe deposition
and growth conditions (such as signicantly lower substrate temperatures or increased substrate bias) results in the growth of
poly-crystalline multilayer structures which quite often show a
hardness increase at bilayer modulation periods in the range of
210 nm (similar to the behaviour shown in Fig. 3). These coatings are therefore in the literature also referred to as superlattices.
Many examples of poly-crystalline superlattices showing a superlattice effect (signicant hardness increase as a function of the
multilayer design) are reported for various combinations of isostructural nitride layers (and for combinations of nitride layers of
different crystalline structure as well) [7].
Chu et al. [32,33] reported a pronounced superlattice effect in
reactively magnetron-sputtered TiN/NbN coatings grown on steel
substrates at substrate temperatures below 500 C. They claimed
for a strong control of the bilayer modulation period , of the stoichiometry of the individual nitride layers and for the design of
high-density multilayer structures in order to obtain high hardness values in poly-crystalline superlattices. A moderate change
in the deposition parameters (i.e. of the nitrogen partial pressure) could result in failure for obtaining the superlattice effect.
Furthermore, ion bombardment during lm growth could affect
the composition modulation, defect densities and porosity of the
superlattice structure [32,33]. Signicant hardness enhancement
in TiN/NbN superlattice lms was also reported by Li et al. [34],
who observed maximum hardness values of 39 GPa at a modulation
period of 8.3 nm in lms grown on single-crystal silicon wafers. The
superlattice effect was assigned to be due to the alternating stress
eld in the TiN/NbN superlattice, which resulted from the lattice
mismatch between fcc TiN and fcc NbN. Barshilia and Rajam [35]
identied a specic range of the modulation period  where the
formation of superlattice structures in the TiN/NbN system (with
regard of the deposition conditions applied, such as a substrate
temperature of 400 C) and the superlattice effect were observed.
These coatings exhibited a thermal stability up to 700 C. A detailed
analysis of TiN/NbN coatings with a modulation period of about
7.7 nm deposited on silicon (1 0 0) at a substrate temperature of
100 C [36] indicated a poly-crystalline, (1 1 1) textured, columnar
microstructure (with columns along the growth direction with an
average column size of about 100 nm). HRTEM studies showed a
non-planar nature of the lattice planes which was attributed to
the presence of a sub-grain structure with lattice misorientations
caused by the lattice mismatch between TiN and NbN. Superlattice
structures and superlattice effects with a variation of the coating hardness values have also been reported for TiN/CrN coatings
[3742]. Technologically important material combinations based

on the integration of AlN layers, for example TiN/AlN superlattices

(showing enhanced hardness as well) are described in Section 3
as they make use of the stabilization of hexagonal AlN in a cubic
structure. Other crystalline nitride-based multilayer systems with
superlattice effects not referred to here in detail include TiN/TaN
and other TaN, NbN or MoN based coatings [4345]. A review of
Musil [46] mentions superhard TiC/VC and TiC/NbC superlattice
coatings. Further approaches towards the development of innovative high performance coatings address the design of ternary and
quaternary (or even multi-elemental) multilayer and superlattice
structures. While the integration of metastable layer materials from
the (Ti, Al)N and (Cr, Al)N families is well established today, less
papers are published in this eld in comparison to superlattices
composed of crystalline binary nitrides. Superlattice structures
with more or less pronounced hardness modication were reported
for material combinations like TiAlN/ZrN [47], TiAlN/CrN [4850],
TiAlN/VN [48,5153], TiAlYN/VN [49], TiAlCrN/TiAlYN ([50,51]; a
superlattice effect was not found in this Y-containing system;
these superlattices are listed here however with regard to their
signicant improvement of tribological properties), TiAlN/TiAlCrN
[54], CrAlYN/CrN [55], TiCN/ZrCN [56], and TiHfN/CrN [57]. Single
reports have been published also on superlattice structures of high
hardness or with hardness enhancement for combinations of crystalline carbide and nitride hard materials, for example in WC/TiN
or WC/CrAlN [58,59], and for combinations of crystalline nitride
or carbide with boride materials, for example in TiC/TiB2 , ZrC/ZrB2
and ZrAlN/ZrB2 [6062].
Hardness enhancement in crystalline superlattice structures is
explained by the widely accepted concept of blocking of dislocation
motion at the layer interfaces due to differences in the shear moduli
of the individual layer materials, and by coherency strain causing periodical strainstress elds in the case of lattice-mismatched
multilayer lms [13]. In many material combinations, the evolution
of the hardness as a function of the bilayer modulation period 
shows a characteristic behaviour for all these coatings with maximum hardness values typically obtained for values of  between 2
and 10 nm [13,14]. The high interface density of nanoscale multilayers or superlattice structures contributes to impeding dislocation
motion and dislocation glide across the layer interfaces, which
would require a critical yield stress being related to the difference
in the elastic shear modulus of the individual layer materials [63].
Detailed studies of Barnett and co-workers of mechanical properties of transition metal nitride, metal/nitride and metal/metal
superlattices taking into consideration more realistic assumptions
on a superlattice architecture (for example: different shape of interfaces instead of abrupt, smooth interfaces; allowing an interface
width; dislocation motion within layers as another mechanism of
plastic deformation additionally to dislocation glide across layer
interfaces) resulted in a theoretical description of the strength and
hardness evolution of superlattice systems which gave good agreement with experimental work (with regard to the conditions set
for this model: miscibility of the individual layer materials and
referring only to materials with the same dislocation slip systems)
[64]. According to this model, the strength or hardness of a superlattice structure should (for a wide range of values of the bilayer
modulation period ) be limited by dislocation glide within layers,
but not across layers. The potential for hardness enhancement in
such mulitlayers is directly related to the difference in the shear
moduli of the layer materials. The interface width effect would
become important only for relatively small values of . Chu and
Barnett further mentioned the HallPetch relation not to be a suitable model for the type of superlattices described in their model.
The HallPetch relation was considered to be applicable for multilayer systems composed of materials having different dislocation
slip systems, where stress concentrations at dislocation pileups in

M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

one layer would cause dislocation nucleation in another, neighbouring layer [64]. Considering the ceramic character (due to substantial
amounts of covalent bonds) of many of the superlattice materials,
the overall columnar growth structure resulting from most PVD
processes, the specic kinetic conditions for thin lm nucleation
and growth, nano- and microscale growth defects occurring in most
deposition processes, as well as defects in the coating microstructure, further mechanisms contributing to hardening or softening of
the coatings should be regarded. These include initiation and propagation cracks at various length scales, starting or ending possibly
at grain boundaries or column boundaries [8]. Other features being
relevant for the coating properties are the overall stress state of
the coating, the stress prole of the individual layers of the multilayer, and their interaction with each other, or with interfaces,
dislocations and microcracks.
2.3. Poly-crystalline superlattice thin lms without superlattice
effect
A variety of hard nanoscale multilayer coatings can be grown
with a superlattice structure (as indicated for example by the
corresponding low-angle XRD reections of the coatings) but no
superlattice effect with regard to a signicant variation of the
hardness is observed. Such behaviour was reported for example
on technologically relevant CrN/NbN superlattice coatings developed by Mnz, Hovsepian and co-workers [6567] and other
groups [68,69], but also for TiN/NbN superlattice coatings [70]. The
non-existence of a superlattice hardening effect in the TiN/NbN
coatings (which is in contrast to the results described in Sections 2.1 and 2.2) was explained to be due to microcracking
at grain boundaries under the indenter tip during nanoindentation measurements. Ducros et al. [71] showed a continuous
transition from nanoscale poly-crystalline multilayer coatings to
poly-crystalline superlattice lms in the TiN/AlTiN and CrN/AlTiN
systems. Superlattice structures without superlattice effect have
also been reported in carbide systems, for example in TiC/NbC and
TiC/VC [72,73].
Another interesting material system in this category is the
TiN/ZrN system ([7478], see also the review of Ziebert and Ulrich
[79], and references therein). Both TiN and ZrN exist in the same
cubic face-centered crystal structure with a lattice mismatch of
7.1% (aTiN = 0.424 nm, and, aZrN = 0.457 nm, according to JCPDS 381420, and, JCPDS 35-0735, respectively). Moreover, TiN and ZrN
exhibit similar properties such as high hardness and high melting
point. The shear moduli of TiN and ZrN are 1.96 1011 N/m2 and
2.51 1011 N/m2 , respectively [80], which gives a difference in the
shear moduli of 28%.

325

In the following, results obtained by the authors for the epitaxial growth of nanoscale TiN/ZrN multilayer coatings on Si wafer
and cemented carbide by reactive dc magnetron sputtering are
described (for detailed information see [76,79]). The coatings were
deposited with an industrial sputter equipment in a stop-and-go
mode, which means, that the substrate samples were coated in front
of one cathode and then moved to the other cathode for deposition
of the next layer. By this method, well-pronounced sharp interfaces between the TiN and ZrN layers and layer numbers between
2 and 1000 at an overall coating thickness of 4 m (corresponding
to bilayer modulation periods down to 8 nm) could be realised. The
individual TiN and ZrN layers were stoichiometric, and the coating
showed a ne columnar morphology. High-angle XRD analysis in
a BraggBrentano experiment showed a poly-crystalline structure
of the TiN and ZrN layers and indicated a heteroepitaxial growth of
ZrN on TiN: reections of the (1 1 1), (2 0 0), (2 2 0), (3 1 1) and (2 2 2)
orientations of the fcc ZrN structure and (1 1 1), (2 0 0) and (2 2 0)
reections of the fcc TiN structure were identied. Fig. 4 exemplarily shows results of the TEM analysis of a TiN/ZrN multilayer
of 20 individual layers (bilayer period 400 nm): The selected area
diffraction (SAD) patterns conrm the (locally) epitaxial growth
of ZrN on TiN. The lattice constant derived from the TEM analysis
resulted in values of aTiN = 0.41352 nm and aZrN = 0.4568 nm, which
are in good agreement with the above mentioned values, indicating nearly stress-free fcc TiN and ZrN lattices. The HRTEM image in
Fig. 4 shows a ne microstructure with pronounced column boundaries (with columns diameters between 450 and 600 nm). From the
enlarged picture of an interface between a TiN and ZrN layer it can
be clearly seen that the lattice fringes grow through the TiN layers, ZrN layers and across their interfaces, which indicates that the
TiN/ZrN coatings grew epitaxially. The interface width between the
TiN and ZrN layers is in the range of 2 nm, and, the interface is not
fully sharp. Fig. 5 shows both the Vickers microhardness and the
reduced Youngs modulus determined by nanoindentation for the
lms as a function of the number of individual layers. A superlattice effect is not observed for these coatings; the hardness increases
with increasing number of layers (corresponding with a decreasing bilayer period) and then remains nearly unchanged between
100 and 1000 layers (corresponding to bilayer periods between 80
and 8 nm). The Youngs modulus increases with increasing number of layers, reaches a maximum value around 50100 individual
layers (corresponding to bilayer periods between 160 and 80 nm)
and then decreases drastically with increasing the number of layers from 100 to 1000 (corresponding to a bilayer periods between
80 and 8 nm). At high numbers of individual layers (low bilayer
modulation period) the TiN/ZrN coatings exhibit a reduced Youngs
modulus and a less ductile behaviour at the nanoscale which could

Fig. 4. Transmission electron microscopy analysis of a TiN/ZrN multilayer coating of 20 individual layers at a total thickness of 4 m. Left side: Selected area diffraction
pattern and HRTEM image of an interface region between TiN and ZrN layers. Right side: HRTEM image of a column structure and column boundary.

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M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

and is intensively stimulated by the work of Veprek et al. on superhard nanocomposite structures in the TiSiN and other systems
[81,82].
Chen et al. [83] reported on the integration of amorphous
SiNx layers in TiN/a-SiNx multilayers. Under certain conditions the
columnar growth of the coatings was completely suppressed. A
remarkable hardness enhancement and residual stress reduction
(compared to pure TiN coatings) was observed for a thickness of
0.5 nm of the a-SiNx layer (while the thickness of the TiN layer
was xed at 2.0 nm). Yau et al. [84] observed an increase in the
hardness of nanocrystalline TiAlN/amorphous Si3 N4 multilayers
at bilayer periods around 20 nm. A similar behaviour on TiAlN/aSi3 N4 nanolaminated coatings was reported recently by Park et
al. [85] who identied the thickness of the amorphous layer as
the most important factor to control the coating properties. Maximum hardness values were found for a 0.3 nm thick amorphous
layer at bilayer periods of 3.5 nm. Other material combinations
(not referred to here) intended for the development of hard, wearresistant multilayer coatings for tribological applications include
the incorporation of amorphous or diamond-like carbon layers or
even completely amorphous multilayer lms.
Fig. 5. Vickers microhardness and Youngs modulus of TiN/ZrN multilayer coatings
as a function of the layer number (total lm thickness: 4 m).

3. Nanoscale multilayer coatings with epitaxial

stabilization effects

indicate a more brittle character probably caused by microcracking at the pronounced column boundaries. Soe and Yamamoto [74]
observed a minimum in hardness and elastic modulus of (2 0 0) oriented TiN/ZrN superlattices at a bilayer modulation period of 3 nm.
The hardness of their lms decreased signicantly if the bilayer
period was less than 8 nm (bilayer periods below 8 nm in our model
would require a higher number of layers which is difcult to realize with the experimental stop-and-go deposition procedure). They
suggested elastic anomalies in terms of the coherency strain caused
by interfaces as explanation for this behaviour. In contrast to these
ndings, Tavares et al. [75] found a moderate hardness increase
in TiN/ZrN multilayers at a bilayer period of 7.5 nm (for coatings
deposited in a rotation mode); however not enough information on
the coating microstructure is available in this case. Rizzo et al. [77]
analyzed their TiN/ZrN superlattices by nanoindentation and found
a minimum value for the indentation depth at a bilayer period of
9 nm. Xu et al. [78] found a minimum in hardness and elastic modulus in TiN/ZrN superlattices at a bilayer period around 8 nm; for
values of the bilayer period between 15 and 30 nm the hardness
and elastic modulus were nearly unchanged. They discuss the formation of an interlayer of a solid solution of Tix Zr1x N under the
deposition conditions applied in their experiments; this interlayer
would form new interfaces in the multilayer and clearly impact the
mechanical properties of the coatings.

Nanoscale multilayer structures composed of materials having

different crystal lattice structures (under thermodynamic equilibrium conditions) quite often tend to form coherent interfaces
between the layers through epitaxial stabilization of one material
in the lattice structure of the other one. This means, the thermodynamically unfavourable state of incoherent interfaces is balanced
by the growth of a metastable structure for one of the layer materials that is able to build a coherent interface with the other layer.
Consequently, the minimisation of the interfacial energy is the driving force behind the epitaxial stabilization effect. Such metastable
structures are usually observed in extremely ne-scale superlattice structures at very low layer thickness and have been reported
for various nitride, carbide and mixed nitride/carbide multilayer
systems. Recent developments address the stabilization induced
crystalline growth of layer materials that (under the usually applied
deposition and growth conditions of most PVD processes) would
grow in an amorphous structure. It has to be mentioned that, apart
of the stabilization of a crystal structure in some material systems,
the stabilization of a textured orientation can occur as well (i.e. the
new layer material would grow in a texture of the other, template
material or in another texture of its own structure in order to minimise the interfacial energy). Texture stabilization was observed
for example in nanoscale TiC/TiB2 multilayers where TiC layers
grew in a (1 1 1) texture on the (0 0 1) oriented TiB2 layers [86].
In the following the focus is on the structure stabilization in hard
multilayer coatings. (Note: In a strong physical sense the wording epitaxial stabilization might not always be used fully correct;
often poly-crystalline substrate materials are used or the coatings
are poly-crystalline ones with a columnar morphology, but with
local epitaxy within the columns. For the latter reason, the wording epitaxial growth is well accepted for such coatings in the
thin lm community as well.) In this section we continue the phenomenological description of growth effects in multilayer thin lms
according to the comments made in the introductory paragraph of
the previous section.

2.4. Multiphase multilayer thin lms

This emerging new approach to hard multilayer coatings by
integration of an amorphous layer material is briey overlooked
here only. An important factor for the development of multiphase
crystalline/amorphous multilayers refers to the periodical interruption or even complete suppression of the columnar growth
in PVD coatings. The columnar grain boundaries often act as
sites for crack initiation resulting in failure of the coatings. By
introducing a few nm thin amorphous layers of boron carbide
(a-B4 C) in TiC/TiN multilayer coatings, Holleck and Schier [5]
could improve the coating properties and performance signicantly by forcing the crystalline layers to periodically re-nucleate
on the amorphous interface layer. It has to be mentioned that the
research on nanocrystalline/amorphous multilayer coatings was

3.1. Stabilization effects in nitride multilayer systems

The most prominent example of this class of materials is the
TiN/AlN system. It has found considerable scientic and technical

M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

interest since the rst reports on the formation of cubic AlN in

TiN/AlN superlattice structures were published nearly simultaneously by Setoyama et al. [26] and Madan et al. [27] one decade
ago. AlN under thermodynamic equilibrium conditions forms a
Wurtzite-type structure (hexagonal), while TiN forms a NaCl-type
structure (cubic).
Setoyama et al. [26] reported on the growth of AlN in a
metastable NaCl-type structure on Si wafer and cemented carbide
substrates for arc ion-plated TiN/AlN superlattice lms at modulation periods below 3 nm. The coatings showed a strong superlattice
effect, i.e. a signicant increase of the hardness with decreasing
modulation period. A maximum in the hardness values (about 1.6
times that of TiN single layer coatings) was obtained at a modulation period of 2.5 nm. The microstructural analysis of a lm with
a modulation period of 3 nm revealed a poly-crystalline superlattice structure with a columnar morphology. The individual columns
were shown to be single crystals with an ordered periodic structure. In the superlattice with low modulation periods ( = 2.5,
3 nm) TiN and AlN exhibited a single-phase cubic structure. In
superlattice lms with larger modulation period ( = 35 nm) TiN
showed a cubic structure, while AlN grew in a hexagonal structure.
Fig. 6 displays some of the original results of Setoyama. Madan et
al. [27] reported on the epitaxial stabilization of cubic NaCl-type
AlN in AlN/TiN superlattices grown on MgO (0 0 1) substrates at
650 C by magnetron sputtering. Epitaxial stabilization of AlN in
the metastable cubic NaCl-type structure was demonstrated with
AlN layer thickness below 2 nm; for AlN layer thickness >2 nm,
the thermodynamically stable hexagonal phase was observed for
AlN.
Since these pioneering works large efforts to understand the
stabilization effect [10,87,88] and to further optimize the TiN/AlN
superlattice architecture and properties [8991] have been made
until today. It is state-of-the-art knowledge that a superlattice effect
(i.e. hardness enhancement) is related to the stabilization effect in
the TiN/AlN system, and, that the stabilization of AlN in a metastable
cubic lattice is successful only for low thickness of the AlN layer.
Increasing this thickness of the AlN layer above a critical value
(about 2 nm) results in a loss of the stabilization and superlattice
effect as the AlN layer transforms to the stable hexagonal phase
[10]. The critical thickness of the AlN layer is dependent on the
sum of the Gibbs free energy GI of the interface of AlN to the template layer (being directly related to the lattice mismatch between

327

AlN and the template layer) and of the Gibbs free energy GAlN of
the AlN lattice (which gives a relation between the G values of
the cubic NaCl-type or hexagonal Wurtzite-type structure in correlation to the thermodynamic conditions such as pressure and
temperature, weighted with the AlN layer thickness). For stabilization of AlN in the cubic structure GI,fcc/fcc (interface energy
for coherent interfaces between two fcc lattices) is lower than
GI,fcc/hex (interface energy for incoherent interfaces between an
fcc and an hexagonal lattice). Simultaneously, GAlN,hex is lower
than GAlN,fcc according to the thermodynamic equilibrium conditions. Similar considerations are described in a model of Barnett
and co-workers [92]. Karimi et al. [93] addressed the correlation
between relative crystallographic orientations of the AlN and TiN
layers and the formation of coherent structures and their impact
on the superlattice effect. For a special architecture of the TiN/AlN
superlattice (i.e. for values of the layer thickness below 10 nm) and
well-dened growth conditions, the formation of a strong (1 1 1)
texture of the superlattice could be adjusted, being a prerequisite
for the stabilisation of AlN in the cubic structure and the formation
of epitaxially coherent structures.
AlN has also been stabilized in the cubic NaCl-type structure in
other multilayer systems like AlN/VN [94,95], AlN/NbN [10], and
CrN/AlN [96]. In AlN/VN superlattice structures the phase transformation of AlN from the epitaxially stabilized cubic NaCl-type
structure to the hexagonal Wurtzite-type structure occurred at critical values of the AlN layer thickness above 4 nm [94]. According
to Li and co-workers [95], this superlattice system shows both a
superlattice effect in hardness variation and a supermodulus effect
(increase of the elastic modulus with decreasing bilayer modulation period) with maximum values both for the hardness and the
elastic modulus achieved at a modulation period of 1 nm. Epitaxial stabilization, sometimes accompanied by superlattice effects,
was observed in a variety of other nitride multilayer systems,
for example in TiN/TaN [9799], TiN/MoN [7], NbN/TaN [100], or
in combination with CNx [7] or even oxynitride materials [101].
Sderberg et al. [102,103] reported the successful epitaxial stabilization of cubic silicon nitride in TiN/SiNx superlattice lms
at a SiNx layer thickness of 0.3 nm. Increasing this value up to
0.8 nm resulted in the transformation of the cubic SiNx phase
into an amorphous (equilibrium) phase. The superlattices with
nanostabilization showed a pronounced superlattice hardening
effect.

Fig. 6. Epitaxial stabilization of fcc AlN in TiN/AlN multilayer coatings. Original results presented by Setoyama et al. [26]. Bright eld (left) and high-resolution (right) TEM
images from a TiN/AlN multilayer with a bilayer period of 30 nm. Dark layers are TiN, light layers are AlN. The growth direction in the picture on the left is from bottom to
top, while in the picture on the right is from left to right.

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M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

3.2. Stabilization effects in carbide, mixed nitride/carbide and

other multilayer systems
In contrast to the intensive work carried out on epitaxial growth
and superlattice effects in nitride multilayer systems, only poor
information is available on similar growth effects occurring in
carbide (or other non-nitride) multilayer material combinations.
This is quite as surprising as materials like SiC or oxides due to
their excellent properties are very interesting candidates for the
design of advanced hard and wear-resistant coatings. In magnetron
sputtering and other relevant PVD methods these materials under
conventionally applied deposition conditions tend to grow in an
amorphous structure (there is however evidence, that under severe
conditions such as high substrate temperature and extremely
strong ion bombardment applied in parallel in magnetron sputtering, crystalline SiC might form [104,105]). The epitaxial stabilization
of SiC in a cubic NaCl-type structure is however a challenging question in thin lm development.
Our group addressed this question as early as in 1999 with
multilayer coatings in the TiC/SiC system [106,107]. In the case
of non-reactive magnetron sputtering from ceramic TiC and SiC
targets, the SiC layers for all deposition conditions applied (i.e. substrate temperature between 300 C and 550 C) grew amorphous,
and, consequently, nanocrystalline TiC/amorphous SiCx multilayer
lms were obtained. Decreasing however the modulation period
of this multilayer system down to 4 nm and below resulted in a
complete intermixing of both TiC and SiC and in the formation of a
nanocrystalline metastable (Ti1x Six )C coating. Changing the deposition method to reactive magnetron sputtering from elementary
Ti and Si targets at a substrate temperature of 400 C, the growth
of the coatings changed signicantly also. Single-layer SiCx thin
lms grew in a hexagonal structure when the carbon concentration X exceeded a critical value, otherwise they grew amorphous.
Applying the deposition conditions of crystalline SiC growth while
forming a multilayer coating with TiC resulted at least in three dif-

ferent microstructures: For large values of the bilayer modulation

period (i.e. >23 nm) the multilayer was composed of nanocrystalline fcc TiC and hexagonal SiCx . For bilayer modulation periods
below 23 nm (and above 4 nm) the hexagonal structure of the pure
SiCx layer disappeared, and, due to intermixing effects between SiC
and TiC, a Ti-containing solid solution (Si1y Tiy )C in a nanocrystalline fcc structure grew. The template layer changed as well to
a Si-containing solid solution of (Ti1x Six )C in the fcc structure
of TiC. Consequently, this multilayer architecture was considered
to have a epitaxially stabilized structure of a SiC-type layer on a
TiC-type layer (see Fig. 7). For bilayer modulation periods below
4 nm, a complete intermixing of both these layers was observed,
and the coating microstructure again was characterized to be a
nanocrystalline metastable solid solution of (Ti1x Six )C (see Fig. 7).
These results clearly imply that besides thermodynamic considerations the kinetic aspects of thin lm growth necessarily have to
be considered for the design of new PVD coatings with improved
properties.
Recently, Li and co-workers [108,109] demonstrated a true
epitaxial stabilization of SiC in a cubic NaCl-type structure in
TiN/SiC superlattice coatings. Stoichiometric TiN and SiC lms
were deposited by magnetron sputtering from ceramic compound
targets without additional substrate heating or bias-induced ion
bombardment in order to avoid interdiffusion between the layers. Depending on the nanoscale thin lm architecture (i.e. for a
thickness of the SiC layer below 0.8 nm and a thickness of the TiN
layer of 4.3 nm) a well-dened compositionally modulated structure and a poly-crystalline fcc microstructure were identied. The
lattice fringes grew across the individual TiN and SiC layers supporting the mutual epitaxial growth of SiC and TiN (see Fig. 8). For these
coatings a remarkable superlattice hardening effect with maximum
values of the hardness in the range of 60 GPa was observed. Similar
structure stabilization including a superlattice hardening effect was
reported by the same group to occur in TiN/SiO2 multilayer coatings
[110]. To complete this picture, it should be mentioned, that already

Fig. 7. Nanostabilization and growth effects in reactively magnetron-sputtered TiC/SiC multilayer coatings. For a bilayer modulation period below 4 nm, a solid-solution
strengthened nanocrystalline (Ti1x Six )C lm is formed, while for modulation periods between 4 nm and 23 nm, epitaxial stabilization of fcc SiC-like layers, (Si1y Tiy )C, on
fcc TiC-like layers, (Ti1x Six )C, occurred.

M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

Fig. 8. Epitaxial stabilization of SiC in cubic structure and superhardness effect in

magnetron-sputtered TiN/SiC superlattice coatings according to Li and co-workers
[108,109].

in 1996 Sproul had claimed for the formation of hard oxide superlattice coatings [111], a subject which may nd much more attention
in the coming years due to signicant progress made in the PVD
deposition technology (but being already an intensively developing research eld in microelectronics: just take the development
of perovskite-type ABO3 oxides with A, B being metals such as Sr,
Ti, La, and their superlattice structures as an impressive example
[112,113]).
4. New approaches in the design of hard and wear-resistant
nanoscale multilayer lms
In this section we will briey describe some new approaches
towards the engineering design of advanced hard and wearresistant nanoscale multilayer coatings. The concepts presented are
of course selectively chosen and do not provide for an evaluation of
their expected value and applicability. Generally, two philosophies
will be regarded: the integration of new materials with advanced
structural and functional properties into a multilayer compound,
and, the objective of achieving benets in the multilayer properties from extremely ne-scale ordering processes occurring in
such novel multilayer systems. Two examples of innovative multilayer designs, based on the integration of advanced metastable
layer materials and new nanocomposite thin lms are suggested.
4.1. Integration of advanced hard metastable materials in
multilayer coatings
The issue of multilayer coatings containing metastable solid
solutions was already discussed in the previous sections of this
paper. The most prominent examples having achieved industrial

329

relevance are related to the incorporation of a metastable fcc

(Ti1x Alx )N layer in a multilayer system. With regard to the
exceptional properties of these coatings it is quite reasonable to
investigate if similar coatings showing even superior properties
can be designed.
Here results of our group on the formation of new metastable
phases with promising mechanical properties in the material system VAlCN are presented. The rationale behind the formation of
metastable phases in PVD thin lms was described by Holleck [114].
Thermodynamic considerations and calculations following this
rationale led to the conclusion that metastable phases should form
between VC and AlN, and, that a material with a covalent bonding
character (AlN) should be able to grow in a metal-like structure (as
of VC) if the kinetics of the deposition would be adjusted properly.
One key parameter determining the growth of PVD coatings is the
diffusion length of atoms within the forming lm. This parameter
can be tuned by controlling for example the substrate temperature, the substrate bias induced ion energy deposited to the coating,
and the uxes of the lm forming particles. For a given composition in the VAlCN system different coating microstructures can
be designed in dependence of the diffusion length, ranging from
completely amorphous structures to metastable mixed crystals and
two-phase nanocomposites. VAlCN coatings were deposited by
non-reactive r.f. magnetron sputtering from an isostatically hotpressed compound target of a previously calculated composition
of 60 mol% VC and 40 mol% AlN with a diameter of 75 mm in a
Leybold Z 550 unit (in the following referred to as VC/AlN 60/40).
Substrate materials used were Silicon (1 0 0) and cemented carbide plates. The r.f. target power was varied between 5.65 and
11.3 W/cm2 , the substrate temperature was 150 C or 220 C, respectively, and the substrate bias was varied between 25 and 200 V.
Under certain deposition and growth conditions (i.e. substrate
temperature: 220 C, substrate bias: 175 V), fcc metastable solidsolution strengthened (V0.3 Al0.2 )(C0.3 N0.2 ) coatings were deposited
(the elemental composition of the lms was determined by electron
microprobe analyses). Fig. 9 displays the results of the transmission electron microscopy. The diffraction pattern is clearly related
to a cubic face-centered poly-crystalline microstructure, while the
bright eld and dark eld images show a dense, ne-scale columnar
morphology of the coatings. These metastable coatings showed a
strong solid-solution strengthening effect: their Vickers microhardness was measured to be about 3200 HV0.05 which is signicantly
above the values determined for pure VC and AlN thin lms which
have been deposited under the same conditions as well (Vickers
microhardness of VC: 2300 HV0.05 , and of AlN: 1200 HV0.05 ). These
coatings have not yet been integrated into multilayer arrangements, but seem to have some potential for the design of multilayer
coatings with superior properties if compared to their constituent
equilibrium phases.
The formation of such metastable phases can occur in many
material systems. Again, the most intensively investigated system in this regard is the TiAlN system due to the formation
of the (Ti1x Alx )N thin lm materials with outstanding mechanical properties and thermal stability. While these properties
were early recognized and are widely technically exploited today
[115118], only recently Mayrhofer et al. explained the basic
mechanism behind the high hardness and high thermal stability of these coatings [119121]. For an AlN mole fraction X below
0.7, the (Ti1x Alx )N coatings crystallize in a supersaturated cubic
NaCl-type structure where Al substitutes for Ti. The metastable
cubic (Ti1x Alx )N structure decomposes during annealing forming extremely ne-scale precipitates of cubic TiN and cubic AlN
domains, before phase transforming into the thermodynamically
stable constituents (i.e. cubic NaCl-type TiN and ZnS-Wurtzite-type
AlN). The formation of the cubic TiN and AlN precipitates, building

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M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

Fig. 9. Transmission electron microscopy analysis of magnetron-sputtered metastable fcc (V0.3 Al0.2 )(C0.3 N0.2 ) coatings. Bright eld (left) and dark eld (right) images indicate
a ne-scale columnar morphology. The diffraction patterns are characteristic of a cubic NaCl-type structure.

coherent interfaces with the cubic (Ti1x Alx )N matrix, results in a

hardness enhancement by providing additional obstacles for the
dislocation movement (see Fig. 10). Mayrhofer et al. found such
thermally induced self-organisation effects resulting in temporary
hardness increase as well in metastable TiBN thin lms, based
here on segregation processes [122,123]. These examples clearly
show the potential for optimization of properties in thin lms due
to nanoscale ordering effects. The thermal stability of metastable
materials and the effective design of new nanolaminated composite coatings (i.e. multilayer coatings with extremely ne-scale
structural ordering) are crucial issues of future research in this
eld.
4.2. Integration of multiphase nanocomposite materials in
multilayer coatings
While nanocomposite materials are in the focus of materials
science in nearly all scientic and engineering disciplines [124],
specic multiphase nanocomposite materials composed both of
nanocrystalline and amorphous phases still are an emerging but

Fig. 10. Hardening effects in metastable thin lm materials due to structural ordering through the formation of temporary coherent nanoscale precipitation domains
during thermally induced decomposition of supersaturated fcc (Ti1x Alx )N coatings
according to Mayrhofer et al. [119]. The diagram shows the hardness H as a function
of the isothermal annealing temperature Ta and dynamical DSC measurements of
(Ti0.34 Al0.66 )N and TiN lms.

promising issue. We have developed carbon based (Ti, Al)(N, C)/a-C

nanocomposite thin lms combining nanocrystalline fcc titanium
aluminium carbonitride and amorphous carbon phases in one layer
structure. These coatings were synthesized for example by reactive magnetron sputtering from a TiAl 50:50 alloy target [125127].
Keeping all deposition parameters xed at constant values (i.e.
the cathode power, the substrate temperature, the substrate bias,
and the total gas pressure; the nitrogen gas ow was xed rst at
the optimum condition required for the deposition of the fcc (Ti,
Al)N phase) and varying only the methane gas ow, we observed
the following thin lm microstructures in dependence of the carbon concentration: For a low carbon concentration (below 8 at.%),
a single-phase fcc metastable solid solution of (Ti, Al)(N, C) was
identied. At medium C content (8 at.% < C < 16.5 at.%), isolated carbon nanoclusters at grain boundaries of the (Ti, Al)(N, C) phase
were observed. At higher carbon concentration (above 16.5 at.%)
the (Ti, Al)(N, C) nanocrystals were found to be completely separated from each other by an amorphous carbon grain boundary
network or matrix phase (see Fig. 11). A ve-step growth model
of these coatings was suggested [127]. Disregarding that issues
addressing the growth of such nanocomposite coatings require
more detailed experimental and theoretical research work, one can
clearly state that the specic design of such coatings by completely
covering nanocrystals with an amorphous phase (which means by
introducing new phase boundaries) might be a tool to optimize
both hardness and toughness in a coating by generating an elastic coupling between hard nanocrystals via sp2 - or sp3 -hybridized
carbon atoms. It was shown that both the mechanical and tribological properties (i.e. the Vickers microhardness, the elastic modulus,
and the wear rates and friction coefcients in unlubricated sliding pin-on-disk experiments against steel counterpart materials)
are a function of the carbon concentration, and could clearly be
related to the microstructure of the coatings. Integration of such
nanocomposite materials into multilayer systems can result in very
interesting material properties, as was demonstrated by our group
recently for nanolaminated composite coatings of TiN and (Ti, Al)(N,
C)/a-C layers. Coatings with various bilayer modulation periods,
with a modied ratio of the thickness of both the TiN and (Ti, Al)(N,
C) layer, and with optimized carbon concentration showed an excellent performance in wear studies and cutting tests on ramp copy
milling of hardened A2 cold work steel, comparable to that of conventional (Ti, Al)N-based benchmark coatings [128]. These results
indicate the technological potential of nanocomposite-based multilayer thin lms.

M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

331

Fig. 11. Microstructure of magnetron-sputtered (Ti, Al)(N, C)/a-C nanocomposite coatings as a function of the carbon concentration (schematically and results of transmission
electron microscopy analyses).

5. Concluding remarks
The intensive work on nanoscale multilayer coatings showing
outstanding properties has been reviewed and new suggestions for
the development of advanced coatings are made in this paper. It
was shown that an extremely ne-scale structural ordering at the
nanoscale is a prerequisite for the engineering design of new multifunctional hard and tough coatings. These new nanoscale design
principles include the formation of superlattice structures, epitaxial growth, and stabilization effects [7], age hardening, recovery and
recrystallization processes [129] as well as interfacial engineering
[5] or residual stress management [14].
Considering the great variety of experimental results available
today on hard multilayer coatings, a systematic approach towards
the understanding of the role of special materials, growth conditions, microstructure and resulting properties is required. While a
good database exists for nitride multilayer systems, only selective
information is found for other material combinations. This database
should not only address parameters being relevant for the nucleation and growth of the materials (i.e. plasma conditions, kinetics
of the deposition process) but should also refer to thermodynamic
aspects (i.e. phase relations, energetic states of interfaces, grain and
phase boundaries).
The elastic and plastic properties of multilayer coatings (or
their hardness and toughness) today are critically discussed versus dislocation motion and various effects promoting or impeding
dislocation motion [4,14]. It is generally accepted that a nanoscale
grain growth and coherent layer interfaces (as well as a reduction of a columnar morphology on the microscale) can result in
a signicant hardness enhancement. Taking into account however the suggested limitation of the applicability of the HallPetch
relation [130,131] and the fact, that many hard materials integrated in multilayer lms have strong covalent bonds, aspects
related to the deformation of ceramic materials (i.e. crack initiation,
crack propagation, reduction of crack energies) and mechanisms of
toughening of ceramics should be considered seriously in theoretical modeling [8,132,133]. Correlations between elastic properties,
fracture toughness, residual stress and macroscopic thin lm properties (i.e. interactions between stress elds and dislocations or
cracks) require more detailed research work in order to understand the deformation mechanisms in nanostructured coatings.

The identication and modeling of stress states and stress distribution proles in hard multilayer coatings and their impact
on the micro- and macroscopic properties are of seminal importance in this eld. Stress generation and interaction should be
considered across various scales, considering especially grain and
phase boundaries as well as articial layer interfaces. Thus, models
like the periodic stress eld distribution suggested by Mendidibe
et al. [134] for nanoscale TiN/CrN multilayer coatings or the triaxial stress eld found by Abadias and Tse [135] for textured
TiN lms could be derived, veried and rened. These objectives demand substantial progress on the analytical side as well,
and, advanced characterization methods mostly combined with
complex evaluation and interpretation of the results are needed.
Analytical methods that should provide detailed insight into the
composition/structureproperty relationships of nanoscale thin
lms include advanced highly sophisticated transmission electron microscopy (i.e. energy-ltered TEM), X-ray diffraction (i.e.
the sin2 -method) and further high-resolution X-ray scattering
methods. Nanoindentation analysis also needs special attention
with regard of their interpretation (i.e. modeling of the interaction of stress elds induced under the indenter tip and the
existing stress eld of the coating) and of improving of the experimental procedure. Recently, Ziebert et al. [136] proposed the
small-angle-cross-section (SACS) method offering a new tool for
a high-resolution depth proling of the mechanical properties on
the nanoscale in multilayer coatings in order to obtain information
especially on the interface regions.
Material concepts for the development of multilayer coatings
with advanced multifunctional properties address for example
the integration of new nanocrystalline, metastable, amorphous or
nanocomposite layers and combinations of those. Superimposing
nanoscale gradients in the chemical composition, growth of the
coatings with gradients in the substrate temperature, or interfacial engineering by modulation of the substrate bias induced
intermixing or stress relaxation at layer interfaces may result as
well in an enhancement of physical properties of multilayer thin
lms. Future work may address phase-transformation-reinforced
multilayer systems (i.e. obtaining benecial effects on the mechanical properties by applying high-temperature or stress activated
reversible phase transformations in one layer) or the design of
smart nanolaminated composite systems, i.e. by incorporating

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M. Stueber et al. / Journal of Alloys and Compounds 483 (2009) 321333

functional layer materials such as ferromagnetic FeCoTaN lms,

which could be used as contactless sensing elements indicating
in-situ wear-related effects on the coating microstructure.
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