Adhesion Measurement of Films and Coatings, Vol. 2, pp.

187-204
Ed. K.L. Mittal
0VSP 2001

On the evaluation of coating-substrateadhesion

by indentation experiments

B. ROTHER*
MAT GmbH Dresden, Reisstr. 3, 0 - 0 1 2 5 7 Dresden, Germany

Abstract-An overview of an energy-related approach for the evaluation of depth-sensing indenta-

tion measurements and their application to the evaluation of adhesion-related phenomena of thin
films and coatings is given. As adhesion-related phenomena are considered internal stresses and
crack formation of the coatings as well as an interface specific energy consumption during the
penetration of the indenter into the coating-substrate system. The phenomena are discussed in rela-
tion to experimental effects. Experimental case studies are presented for multilayer structures of
inkjet microheater systems as well as for single and multilayer hard coating systems.

Keywords: Adhesion; coating; depth-sensing indentation measurements.

1. INTRODUCTION
The technological starting point of interest in adhesion of coatings and thin
films is usually the absence of adhesion or, in other words, coating delamina-
tion. Such failure would correlate to the zero point of empirical scales of adhe-
sion and a full-scale value could be the fracture of either the coating or the sub-
strate material. The principles of adhesion measurement (see for example [ 13)
can be classified into (i) destructive principles with the definition of loading
conditions and finding of loading parameters leading to delamination, and (ii)
non-destructive or nearly non-destructive analysis of adhesion-related re-
sponses of coating-substrate systems under defined loading conditions.
The second of the above classifications is of particular importance and it is
the aim of the present paper to show the potential of depth-sensing indentation
measurements as a nearly non-destructive principle for the evaluation of adhe-
sion of physical vapor deposited (PVD) coatings.

* Phone: +49 (0) 351 20772-17, Fax: +49 (0) 351 20772-22, E-mail: rothermmat-dresden.de
188 B. Rother

2. EXPERIMENTAL EVALUATION OF ADHESION

PVD and CVD coatings represent a wide variety of material combinations and
fields of application. The bonding principles between a coating and a substrate are
generally of system specific character and involve both chemical and mechanical
effects.
The response of coating-substrate systems to mechanical loading can, in prin-
ciple, be described in analogy to stress-strain curves of bulk materials with the
stress or fracture limits corresponding to delamination effects. Differences from
the bulk analogue result from the appearance of normal and shear forces, from the
superposition of coating and substrate effects as well as from the limited thickness
of the coating and the interface region.
Typical loading conditions of coating-substrate systems can qualitatively be
classified into elementary loading conditions as shown in Figure 1. Real mechani-
cal loading conditions are usually combinations of such elementary loading con-
ditions with dynamical and thermal effects as well as properties of the actual
coating and substrate materials.

Normal Tangential
Elementary
loading
conditions

Examples

Gas release Internal stress

Tension Friction

1 Pi
Mixed loading
conditions,
examples pP -ae Peeling Indentation

Figure 1. Loading conditions of coating-substrate systems. c: coating; s: substrate; P,?: normal

force; P,: shear force; P,: tension force; P, : friction force; Pp: peel force; P,: indentation force.
 On the evaluation of coating-substrate adhesion by indentation experiments 189

From the elementary loading conditions shown in Figure 1 forces parallel to the
interface with resulting shear stress in the interface region are of particular practi-
cal relevance. In this connection, important effects for coatings and thin films are:
(i) internal coating stresses parallel to the interface as a result of energy deposition
during film growth as well as thermally induced stresses as a result of different
thermal expansions of coating and substrate materials, (ii) friction, scratch or in-
dentation loading of the coatings with resulting force components parallel to the
surface, and (iii) deformation of the substrate. These effects can be quantified by
stress measurement by bending analysis [2] or x-ray diffraction [3], by scratch test
with spallation pattern evaluation [4] or with acoustical emission analysis [ 5 ] ,by
depth-sensing indentation measurements with indentation depths lower than the
coating thickness [6] or higher than the coating thickness with spallation pattern
characterization at the rim of the indent [7] as well as bending tests on coated
samples [ 5 ] .
Ideal adhesion quantification should employ non-destructive measurement
methods to real samples with loading conditions close to the application of the
samples. Depth-sensing indentation measurements with indentation depths
smaller than the coating thickness are close to these ultimate requirements. They
additionally provide an access to investigations of different classes of coating-
substrate systems such as metal or ceramic coatings on metals or on plastics.

3. DEPTH SENSING INDENTATION MEASUREMENTS

Depth-sensing indentation (DSI) measurements with depth resolution in the nm-
range are preferably used for the determination of hardness under load and the
elastic modulus of thin films and subsurface layers (see e.g. [SI). The technique is
based on classical hardness indentation measurements with additional recording
of indenter displacement in dependence of the actual loading. The application of
DSI measurements to the evaluation of adhesion and adhesion-related character-
istics is based on an energetic interpretation of the indentation process [9]. In re-
lation to the present discussion, a short summary of that approach will be given.

3. I . Energetic interpretation of DSI processes

3.1.1. Homogeneous Bulk Materials. The approach is based on the following
assumptions.
h
(i) The displacement energy of the indenter W , = l P d h p with the load P , the
0

penetration depth h,, and the penetration depth at peak load h is converted into
an increase of internal energy within a limited region of the probed material.
This limited sample region is designated as virtual indenter. The concept of a
virtual indenter has recently been confirmed by finite element calculations
[IO].
190 B. Rother

(ii) The virtual indenter is characterized by its volume Viand its outer face area A i
-
as well as by the mean energy densities wv for the volume related increase
of internal energy density and w, for the face area related increase of inter-
nal energy density. For homogeneous materials the virtual indenter is as-
sumed to be in a most general case a segment of a spheroid with the projec-
tion face on the sample surface being determined by the diagonal(s) of the
indent [l 11. A schematic of such model is shown in Figure 2. During penetra-
tion of the real indenter, the virtual indenter expands against the resistance of
the surrounding material and the volume of the virtual indenter is linearly re-
lated to the volume of the sample material replaced by the real indenter.
(iii) The penetration of the real indenter is considered to be quasistationary which
permits to neglect the dynamic effects.
Starting from these assumptions, the balance of the displacement energy of the
indenter with the increase of the internal energy of the sample region designated
as virtual indenter can be written as

W, =wvVi+w, Ai
with Viand A ibeing the volume and the surface area of the virtual indenter, re-
spectively. With respect to Figure 2 and by neglecting the real indenter, the vol-

Figure 2. Schematic illustration of the indentation model with a real and a virtual indenter approxi-
mated by a cut-off of a spheroid. a, b: semi-axes of the spheroid; s: shift of the spheroid center with
respect to the surface of the sample.
 On the evaluation of coating-substrate adhesion by indentation experiments 191

s
U

ume and the surface area of the virtual indenter are Vi= n y 2 d x and
-s

Ai= 2n 1.d- d x , respectively, with

-s
The integrals give for Vithe correlation
/
S2
3- -7 ,
a a
and for A ia transcendental equation which can be approximated by the sum of the
surface areas of one hemispheroid and the circumferential surface of the cylinder
with the radius b and the height s (see Figure 2). This leads to the expression
/ \
a
arcsin ~mj
+ 2nas .

The two semi-axes a and b of the spheroid as well as the shift s of the spheroid
have now to be correlated to the indentation process. To that aim, for pyramidal
indenters and homogeneous sample materials, a linear relation between the two
semi-axes according the equation a = rb with the proportionality factor r is ex-
pected. Simultaneously, for the short semi-axis, a linear relation to the indentation
depth h according to b = kih with the proportionality constant ki is assumed. The
shift s of the spheroid is additionally assumed to be constant during penetration of
a pyramidal indenter into homogeneous materials.
For the energy balance of Eq. 1 we thus obtain the expression

with a polynomial expression for the volume term involving one cubic, one quad-
ratic and one linear term of the indentation depth as well as with the transcenden-
tal expression C(h)of the indentation depth for the surface area term. The expres-
sion is further simplified by the introduction of an indenter specific energy
2- 3
density e, which is e , = - w, n r k i . Equation 2 can now be written as
3

W,=e, (h3+3~h2)-<z(,'t".,.r 3, +w,C(h)

-
192 B. Rother

Eq. 2 can now be applied to the experimentally measurable quantities, load and
indentation depth, by the second derivative of W, in relation to h which is identi-
cal to the first derivative of the load in relation to h:
d2Wd d P
--- s -d2
=6evh+6e,-+ w,-(C(h)) (3)
dh2 dh rki dh2
The contributions of the three additive terms in Eq. 3 to dPldh can be analyzed
by the plot of experimental dPldh values versus h. This approach proves, how-
ever, not to be trivial as the values of P and h are recorded, for the DSI measure-
ments performed, at the limits of digital resolution of the available instruments.
Consequently, a combination of averaging, numerical differentiation and data
smoothing was developed which was designated as differential load and feed
(DLF) analysis. To distinguish the results of this procedure from the pure differ-
entiation dP/dh, the term "DLF plot" was introduced. To indicate the modification
of dP/dh in the scheme of the DLF analysis, the term {dP/dhJDLF is used for the y-
axis designation in the graphs.
The experimental analysis of Eq. 3 with data gained by DSI measurements with
pyramidal indenters showed a linear behavior of the DLF plots for homogeneous
bulk materials [9,12,13]. This experimental result suggests that the surface term
-
of the mean internal energy density increase w, can be neglected in relation to
wv which permits to neglect the contributions of the nonlinear term of Eq. 3
which can now, following an earlier convention [9], be simplified to

The specific energy density e,, is closely related to the hardness under load and
was, therefore, designated as hardness equivalent [9].
3.1.2. Coatings. The above considerations for homogeneous bulk materials hold,
in principle, also for coating-substrate systems. This is illustrated in Figure 3. The
expansion of the virtual indenter within the coating before reaching the interface re-
gion can be described according to Eq. 4 with the values of e,, r, kiand s being char-
acteristics of the coating material. The situation changes after the virtual indenter has
passed through the interface. Its further expansion within the coating is now limited
by the coating thickness h, whereas the expansion in the substrate follows the same
rules as for bulk materials. The volume of the virtual indenter within the coating
equals now the volume V, of a zone of a spheroid defined by the semi-axes a and b
as shown in Figure 2 as well as by the zone thickness which is identical to the coat-
ing thickness h,. The volume of the virtual indenter within the coating Vi,is thus
2
+h,s2 -h,
3
 On the evaluation of coating-substrate adhesion by indentation experiments 193

real indenter
,

bulk approximation
for the expansion
of the virtual indenter
in the coating

virtual indenter

approximation for
the expansion of
the virtual indenter
in layered structures

Figure 3. Schematic illustration of the penetration of a real indenter and the formation of the virtual
indenter in a coating-substrate system.

The basic distinction of Eq. 5 compared to the expansion in homogeneous bulk

materials as described by Eq. 2 is the disappearance of the cubic term of b and
thus also of h.
An expression for the energy balance of the simultaneous expansion of the
virtual indenter in both the coating and substrate, based on the discussion above
and considering the relations between a, b, r, s and h as listed under 3.1.1., can
now be written in analogy to Eq. 2 and the second derivative of that equation in
relation to the indentation depth h gives

with the indices c and s referring to coating and substrate, respectively, and the
indexed terms are analogous to the explanations in 3.1.1. Equation 6 is again a
linear function of dPldh versus h where the slope is determined only by the hard-
ness equivalent of the substrate material. It should once more be noted that Eq. 6
stands for the simultaneous expansion of the virtual indenter in both the coating
and substrate which is identical to the situation after the virtual indenter has
194 B. Rother

passed the interface between coating and substrate. The expected DLF plots of
coating-substrate systems should thus be determined by two successive linear
ranges. Starting with h from zero, the slope of the first range should correspond to
the hardness equivalent of the coating and the slope of the second range to the
hardness equivalent of the substrate. An experimental confirmation for this ex-
pectation is shown in Figure 4.

I I I I I I
400 -

300 -

200 -

coating-substrate system
100 -
- e - - uncoated substrate (HSS)
I .......... regression lines
1 I I I I I

Figure 4. Experimental DLF plot for (Ti,Al)N on hardened high speed steel (HSS) together with the
plot of the uncoated substrate material. e,: hardness equivalent, see Eqs. 2 and 2a.

3.I .3. Coating-substrate Systems. The response of coating-substrate systems to

the penetration of an indenter is a superposition of coating, substrate and interface
effects. The proportions of these individual contributions change with increasing
penetration depth. The DLF plots of coating-substrate systems should, based on
the discussion above, be a combination of two adjacent linear functions as shown
in Figure 4. Deviations from this estimated response can be expected to be caused
by deviations from the model of two independent and homogeneous material
ranges the virtual indenter passes during its penetration into coating-substrate
systems. Phenomena which have to be considered in that connection are internal
coating stresses, crack events and shear stress at the interface and these phenom-
ena are again components of our complex understanding of coating adhesion.
Internal coating stresses have been shown for sputtered TiN coatings to have
effects on the results of DSI measurements in that compressive internal stress
 On the evaluation of coating-substrate adhesion by indentation experiments 195

causes positive vertical shift of the DLF plots [14]. This vertical shift correlates to
the value of the absolute term of the linear equation which is, with respect to Eq.
4, ev ( d r k J . In particular, if the slope of the vertically shifted DLF plots remains
constant, changes of their absolute term will, with respect to Figure 2 and the dis-
cussion in 3.1.1., correlate only to the term s/rk,. This term describes the shape
and shift of the virtual indenter independent of the indentation depth h. The above
discussed changes of the term d r k , thus support the concept of the virtual indenter
which expands against the resistance of the surrounding material with compres-
sive stress in the surrounding material being one component of the resistance. A
quantitative relation could, however, not be determined.
The crack events at the penetration of an indenter into coating-substrate sys-
tems are particularly evident with hard and brittle materials. These crack events
are related to a stress relaxation which corresponds, in the picture of the virtual
indenter, to a decrease of the internal energy density and, consequently, to a
negative slope of the DLF plots. Such negative slopes are part of negative peaks
of DLF plots. The existence of such negative peaks can be seen from the results
published for example in [ 151 where the so-called pop-ins of load-indentation
plots were correlated to crack events under the penetrating indenter. It should be
mentioned, however, that such crack events do not provide information on
whether the crack propagates along the interface or not. The correlation between
the negative peaks in the DLF plots and the crack events in multilayer coatings as
described in [ 161 provides, therefore, no access to the assessment of adhesion
between the layers.
Besides the vertical shift of DLF plots and negative peaks, another important
feature of the curves is a plateau region instead of a bending point between the
coating and the substrate dominated plot ranges as shown in Figure 4. This pla-
teau range was qualitatively discussed in terms of the resistance of the interface
against the penetration of the boundary of the virtual indenter characterized by an
indenter specific energy consumption [6]. The problems with this approach are,
however, the definition of the plateau region as well as a comparison of the results
to other adhesion assessment techniques such as scratch test [6] or Rockwell-C
indent method [ 171.
Hence summarizing, adhesion related features of the DLF curves are vertical
shifts, negative peaks and plateau ranges between the coating and substrate domi-
nated plot ranges. A schematic illustration of these features is given in Figure 5
and the evaluation principle of the energy consumption of plateau ranges as pre-
sented in [6] is illustrated in Figure 6.
196 B. Rother

I negative peak

h, h*
Indentation depth [arb. units] -
Figure 5. Schematic illustration of adhesion-related features of the DLF curves. CR: plot range
where the slope is determined by the coating material; SR: plot range where the slope is dominated
by the substrate material; h l : indentation depth of the real indenter marking the end of the coating
determined plot range CR; h2: indentation depth of the real indenter marking the beginning of the
substrate dominated plot range SR.

h, h2
Indentation depth [arb. units] *

Figure 6. Schematic illustration of the evaluation principle for the energy consumption in relation to
plateau ranges of the DLF plots: Calculation of indenter specific energy consumption by integration
over AP.CR, SR, h , , hl: see Figure 5 ; AP:difference area (= difference force) between the linearly ex-
trapolated coating range of an experimental DLF plot and the plateau range of the experimental plot.
 On the evaluation of coating-substrate adhesion by indentation experiments 197

3.2. Experimental case studies

The investigations in this section were performed with a microhardness tester
with a load range of 0.4 to 1000 mN, a load resolution of 0.2 mN, an indenter dis-
placement resolution of 2 nm and a stepwise quadratic increment of load over 60
steps. The waiting period between the consecutive steps was 1 s. The instrument
was equipped with Vickers, Berkovich or Knoop indenters. The frame compli-
ance of that instrument could be neglected [12] which permits to apply the above
equations without modifications. All experiments were repeated at least five times
and the analysis was conducted on the averaged load-indentation data.
3.2.1. Microheater Systems for Znkjet Arrays. The main component of inkjet ar-
rays is the microheater with multilayer systems consisting of heater, insulator and
conductor materials of different thicknesses. The operation principle of such sys-
tems is a quick overheating of a very small ink volume by thermal contact and an
ejection of the above liquid through a narrow nozzle. Thus the required thermal
shock loads on the microheater are hard operation conditions which require high
level of adhesion between the individual layers. The layers are usually sputtered
in a multistage process with ion cleaning step before each layer deposition. The
early detection of adhesion losses is thus of fundamental importance to the tech-
nology and the performance of the inkjet system. In the framework of a process
quality program, the effects of the ion cleaning processes were determined by DSI
measurements and a subsequent DLF analysis. The DSI measurements were per-
formed with a Knoop indenter.
The following layer systems were deposited with only one section of each wa-
fer being exposed to ion cleaning prior to deposition of the top layer:
1) Si3N4700 nm / HfB2 200 nm / thermally oxidized Si wafer,
2) Si3N4700 nm /A1 600 nm / HfB2 200 nm / thermally oxidized Si wafer,
3) Ta 600 nm / thermally oxidized Si wafer,
4) Ta 600 nm / Si3N41.5 pm / thermally oxidized Si wafer.
Despite the low layer thicknesses a high reproducibility in the DSI measure-
ments could be achieved. The determination of linear ranges in the plots and, con-
sequently, the calculation of a hardness equivalent failed, however, because of the
low thicknesses of the individual layers. Instead, qualitative effects of ion clean-
ing could be shown in the DLF plots. For the systems 1, 2 and 3 the effects of ion
cleaning could clearly be distinguished as a vertical shift of the DLF curves,
whereas for the system 4 no changes for the ion cleaning could be determined.
Typical results for the different layer arrays are shown in Figure 7. An interpreta-
tion of this result will be given in the discussion section.
198 B. Rother

140
120
-5
CI

100
z€ 80
Y

60

0
0 20 40 60 80 100 120 140 160
Indentation depth [nm]
200 l ' i ' l ' l ' l ' l ' l ' i
/
1-1
180 ,/
n 0

E 160 - 0
0
/

L
140
Y

120 -
d
A

= 100 -
T1 after ion cleaning
n
80 - - - - without ion cleaning - ?

60' I I I * I I
0 20 40 60 80 100 120 140
Indentation depth [nm]
Figure 7.Typical DLF plots for the investigated layer arrangements of inkjet systems. Indenter used
for DSI measurements: Knoop pyramid.
 On the evaluatioiz of coating-substrate adhesion by indentation experiments 199

3.2.2. Hard Coatings for Wear Protection. A large field for the application of
PVD and CVD hard coatings is the wear protection of tools and machinery com-
ponents. Typical coating-substrate systems for this purpose consist of coating
materials such as TiN. (Ti,Al)N, or, generally, transition metal nitrides or carbides
and substrate materials such as high speed steel or cemented carbide. The adhe-
sion of the coatings is of substantial importance to the performance of the sys-
tems. Process steps of the deposition with direct relation to coating adhesion are
wet cleaning and ion cleaning prior to deposition as well as ion mixing between
the coating and the substrate by ion bombardment during interface formation.
The efficiency of wet cleaning procedures (combination of hydrocarbon
cleaning with electrochemically enhanced degreasing) was analyzed in [ 171 for
magnetron sputtered (Ti,Zr)N coatings deposited on hardened high speed steel.
Prior to deposition, the samples were exposed to three different wet cleaning pro-
cedures, and the deposition of the (Ti,Zr)N coatings was performed in one run
with identical parameter sets. The different wet cleaning procedures could thus be
expected to affect mainly coating adhesion with only minor influence on other
properties of the coating-substrate systems. The expected effects were analyzed
by DSI measurements with subsequent DLF analysis as well as by Rockwell-C
indentation tests with a semiquantitative evaluation of the delamination patterns
of the coating at the rim of the indent. Typical DLF plots are shown in Figure 8
where the dotted and dashed auxiliary lines shown in the bottom diagram are in
relation to the scheme given in Figure 6 and indicate the area over which integra-
tion is performed to calculate the specific energy consumption for the penetration
of the virtual indenter boundary through the interface. A summary of these results
together with the evaluation of the Rockwell-C indents is given in Table 1.

Table 1.
Adhesion evaluation for (Ti,Zr)N coatings on high speed steel of different wet cleaning stages [16].
Calculation results of a specific penetration energy of the virtual indenter through the interface and
semiqualitative evaluation of Rockwell-C indents

Sample Wet cleaning intensity” ed in nJ RockwellLC adhesion class2’

A 11 cleaning steps 0.18 HF 3
B 10 cleaning steps 0.22 HF 4
C 3 cleaning steps 1 .O HF 5
ed:Specific penetration energy of the virtual indenter through the interface.
’ ) A: 1 1-stage procedure of ultrasonically enhanced hydrocarbon cleaning and electrochemical

degreasing. B: As for A, without neutralization between cathodic and anodic degreasing. C: 3-stage
procedure of ultrasonically enhanced hydrocarbon cleaning.
*) Classification numbers according to [ 7 ] .
200 B. Rother

Original plots
-E 600 1
I
$
Y
400

2 200
--- - - - .- C
I 1 I , I I

- I I I
- ------- .

I
Regression lines (CR)
I I I

0.0 0.2 0.4 0.6 0.8 1.0

Indentation depth [pm]
Figure 8. Typical DLF plots for (Ti,Zr)N coatings identically deposited on hardened high speed
steel with different wet cleaning stages prior to deposition. Wet cleaning efficiency decreases from
A to C. The numbers in parentheses are the coating thicknesses. Indenter used for DSI measure-
ments: Vickers pyramid.

Besides wet cleaning, ion cleaning is a further process step in PVD which is di-
rectly linked to adhesion. The effects of ion cleaning time have been analyzed in
connection with sputter deposited TiN on hardened high speed steel. For this pur-
pose, the samples were prepared with identical surface finish and wet cleaning
procedures. Two samples were placed in one deposition run and each of them was
 On the evaluation of muting-substrate adhesion by indentation experiments 201

exposed for different durations to an Ar ion etch at -300 V substrate bias. The
samples were then identically coated by magnetron sputtering [ 181. The effects of
the different ion cleanings on adhesion were evaluated by DSI measurements and
DLF analysis. The results of these investigations are shown in Figure 9. The char-
acteristic result for all investigated samples was the slight but reproducible verti-
cal shift of those plots with lower cleaning time.

I I I I I

-E
-

-
I
+
z -
U
E
-

-
11 min ion cleaning -
1 min ion cleaning
-0 '
- _ e - - ~

I I I

0.0 0.2 0.4 0.6 0.8

Indentation depth [pm]
Figure 9. Typical DLF plots for TiN coatings on hardened high speed steel (HSS) deposited after
different ion cleaning times, Indenter used for DSI measurements: Berkovich pyramid.

A powerful tool for the increase of adhesion between PVD coatings and metal-
lic as well as ceramic substrates is the high energy ion bombardment during the
interface formation, Ion energies in the range of some keV are thereby suitable to
initiate implantation and recoil implantation of the film forming particles into the
substrate material which increases generally the potential for increased adhesion
[19]. This process step was again investigated with respect to its effect on DSI
measurements. For this purpose, different high speed steel samples were arranged
in pairs in the deposition chamber and only one of them was exposed to an Ar ion
bombardment during the first minute of TiN deposition by magnetron sputtering.
Before and after the high energy ion bombardment the samples were treated iden-
tically. A typical result for a pair of samples coated under identical parameters ex-
cluding the high energy ion bombardment during interface formation is shown in
Figure 10. A typical result of these investigations was again a vertical shift in the
DLF plot for the sample which was deposited without ion bombardment during
the formation of the interface.
202 B. Rother

250
n

E
1
200
t
-E 150
LL

.----
Regression lines
for the substrate material

0.0 0.1 0.2 0.3

Indentation depth [pm]
Figure 10. Typical DLF plots for TiN coatings on hardened high speed steel (HSS). Deposition with
and without 10 keV Ar-ion bombardment during interface formation. Indenter used for DSI meas-
urements: Vickers pyramid. IBAD: Ion Beam Assisted Deposition.

3.3. Discussion
The results presented here are a summary of the work on the investigation of em-
pirical correlations between adhesion-relevant PVD process steps and features of
the response of coating-substrate systems to indentation experiments. This re-
sponse was analyzed by an energetic interpretation of the indentation process with
the first derivative of the load in relation to the indentation depth plotted versus
the indentation depth. The plot features particularly considered in relation to ad-
hesion were (i) vertical shifts which could be expected to correlate with internal
stresses, (ii) negative peaks which are known from the literature to correlate to
crack events, and (iii) a plateau region between the DLF plot ranges dominated by
the coating and by the substrate responses. An illustration of these features was
given in Figure 5 .
The dominating effect of the above features was the vertical shift of the DLF
plots. The positive shifts thereby correlate with an expected reduced adhesion
between the coating and underlayer. This effect is very important for hardness
measurements on coatings as it is in contradiction to the generally acknowledged
Buckle-rule which claims that the effect of the substrate is relevant to hardness
values for indentation depths larger than 1/10 of the coating thickness [20]. The
 On the evaluation of coating-substrate adhesion by indentation experiments 203

results illustrated in Figures 9 and 10 and particularly in Figure 7 show that the ef-
fects of the interface are already evident at the beginning of the penetration proc-
ess. Compared to conventional hardness calculations as load per area, these posi-
tive shifts are identical to higher hardness values.
At the present state, the vertical shift of the DLF plots as an effect of adhesion
can be discussed in relation to compressive stress in the coatings. This correlates
to earlier results with TIN coatings deposited with different bias voltages gener-
ating different internal stresses which were determined independently from the
DSI measurements [ 141. The correlation between internal coating stress and adhe-
sion follows from a qualitative interpretation of ion enhanced film growth where
the ions are generally assumed to generate internal stress in the growing film [21].
This stress could be balanced by the substrate, and the transformation of the
coating stress to the substrate is the more efficient the better the interface perfec-
tion is. A reduced interface perfection thus leads to accumulation of internal stress
in the coating which again correlates with the origin of the vertical shift of the
DLF plots as discussed above.
The consideration of the negative peaks in the DLF plots as crack events was
introduced above as a further feature for an evaluation of adhesion effects. These
negative peaks do not, however, distinguish between the crack propagation along
or perpendicular to the interface. The negative peaks in the DLF plots are thus a
more comprehensive criterion of coating-substrate systems. Therefore, in the pre-
sent paper it was excluded from an extended discussion.
The plateau ranges in the DLF plots of coating-substrate systems was the feature
of the plots which was first investigated for quantitative correlations with interface
effects [6]. The reliability of the suggested quantification procedure depends, how-
ever, on the reliable determination of the integration boundaries and this is not fully
solved yet [22]. The application of plateau criterion to the quantitative evaluation of
coating adhesion is, therefore, the subject of further investigations.

4. CONCLUSIONS

The results presented illustrate the state of adhesion assessment by depth sensing
indentation measurements with an energetic evaluation of the load-indentation
data. It was shown that the results were particularly suitable for comparative as-
sessment of interface effects. The sensitivity of the approach to interface effects is
dependent on the nature and intensity of the effects as well as of the material
combinations considered.
Effective assessments of adhesion were demonstrated for multilayer arrange-
ments of inkjet systems. Application of the approach to hard coating evaluations
was also demonstrated. At this stage, the approach can already be considered as a
useful tool for adhesion assessments. Further developments of the approach re-
quire further understanding of the model of the virtual indenter combined with
suitable experimental investigations.
204 B. Rother

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