Surface & Coatings Technology 434 (2022) 128224

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Surface & Coatings Technology

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

Evaluation of stress and energy relief efficiency of ZrN/Ti and ZrN/Zr

Jia-Hong Huang *, I-Sheng Ting, Ting-Wei Zheng
Department of Engineering and System Science, National Tsing Hua University, Hsinchu 300, Taiwan

A R T I C L E I N F O A B S T R A C T

Keywords: The purpose of this study was to investigate the extent of stress relief (Δσ%) and energy relief efficiency (ξtot) of
Stress relief metal interlayers in bilayer ZrN/Zr and ZrN/Ti thin films using an energy balance model based on the concept
Metal interlayer that the stored elastic energy in the ZrN coating could be partly relieved by the plastic deformation of metal
ZrN thin film
interlayer. ZrN/Zr and ZrN/Ti specimens with different thicknesses of metal interlayers ranging from 100 to 300
Energy relief
Plastic deformation
nm were deposited on Si substrate using unbalanced magnetron sputtering. ZrN/Ti specimens were also
deposited at different substrate bias voltages for investigating the energy relief efficiency by Ti interlayer under
different stress levels in ZrN. The metal interlayers, Zr and Ti, were selected due to their different strain hard­
ening behavior. Laser curvature method (LCM) and average X-ray strain combined with nanoindentation tech­
nique were employed to accurately measure the residual stresses in the entire specimen and the ZrN coating,
respectively. Experimental results showed that Δσ% was more significant by Ti interlayer than by Zr interlayer.
Δσ% of the entire specimen increased with interlayer thickness, while decreased with increasing stress of the top
ZrN layer. The energy balance model was employed to evaluate ξtot by the interlayers. The contributions of
energy relief from the ZrN coatings (ηZrN) and bending curvature relaxation of Si substrate (ηSi) could be
separately assessed by the model. The results revealed that ξtot decreased by increasing Zr or Ti interlayer
thickness, where the energy relief was mainly contributed from ηSi for ZrN/Zr specimens, while ηZrN was sub­
stantial for ZrN/Ti specimens, and there was an optimum interlayer thickness close to 100 nm, by which ξtot
could reach up to 79.0 and 83.1% for Zr and Ti interlayers, respectively. For the ZrN coatings with different stress
level ranging from − 2.87 to − 3.94 GPa, the variation of ξtot was less distinct, ranging from 39.1 to 48.8%, and
the energy relief was mostly from ηZrN, except for σZrN close to − 4 GPa, where the energy relief was mostly from
ηSi. Although ξtot could serve as a better measure than Δσ% in evaluating the effectiveness of a metal interlayer,
ηZrN and ηSi are the critical indexes that could reveal the actual energy relief in the hard coating. It is found that
ηZrN and ηSi are related to the strength coefficient (k) of the interlayer. Therefore, in selecting a metal interlayer,
it should be considered not only the capacity of energy absorption (Wp,max) but also the malleability (k) of the
metal.

1. Introduction
Due to the excellent mechanical properties, high thermal stability
and superior corrosion resistance, transition metal nitride (TMeN) thin
films and coatings, such as TiN and ZrN, are widely used as the pro­
tective coatings to prolong the service lifetime of the substrate materials
[1]. However, the hard coatings deposited by physical vapor deposition
usually possess high residual stress that may cause adhesion failure or
fracture at the film/substrate interface [2–4]. Moreover, the loading
stress in the mechanical processing may exert an additional stress on the
coating, and thereby increasing the wear rate of the coating [5,6].
Therefore, the residual stress issue should be properly solved especially
for the coatings applied under heavily mechanical and thermal loading.
Residual stress can be controlled by adjusting the deposition pa­
rameters that affect the film growth mechanism [7], by which the de­
fects are reduced and thereby lowering the stress. For the sputtering
process of TMeN thin films, working pressure, substrate bias, and sub­
strate temperature are the parameters commonly used to control the
microstructure and the residual stress of thin films [3,8,9]. However, the
optimization of deposition parameters is usually time consuming and
costly in the practical processing. Alternatively, introducing a metal
interlayer to alleviate the stress in hard coatings is commonly adopted in
industry. In addition to stress relief, the metal interlayer, such as Ti, may
dissolve oxygen and remove the native oxide on the substrate surface,

* Corresponding author.
E-mail address: jhhuang@ess.nthu.edu.tw (J.-H. Huang).

https://doi.org/10.1016/j.surfcoat.2022.128224
Received 12 December 2021; Received in revised form 14 January 2022; Accepted 5 February 2022
Available online 10 February 2022
0257-8972/© 2022 Elsevier B.V. All rights reserved.
J.-H. Huang et al. Surface & Coatings Technology 434 (2022) 128224

thus increasing the adhesion [10].The formation of an inter-mixing zone 2. Theoretical basis
is also conducive to the adhesion strength [11]. In practical applications,
the interlayer thickness for stress relief is usually empirically designed The stress relief of a hard coating by introducing a metal interlayer
ranging from 50 to 300 nm. However, due to the difficulty on measuring can be considered as an energy-transfer process, where the stored elastic
the stress in thin films, the stress relief is normally attributed to the energy in the hard coating is transferred to the interlayer and balanced
plastic deformation of metal interlayer without further quantitatively by the plastic work of the interlayer. The stored elastic energy per unit
modelling. area in the hard coating can be expressed as [31]
The issue of stress relief by metal interlayer has been extensively ( )
studied in the past two decades [12–23]. The interlayer can act as a 1 − ν2f
GS = σ2f hf , (1)
compliant (or buffer) layer to reduce the transfer of shear stress to the 2Ef
coating/substrate interface [10,20]. Thermal stress can be minimized by
matching the thermal expansion coefficients of the interlayer with the where Ef and νf are the Young's modulus and Poisson's ratio, and hf and σ f
coating [13,24]. Previous study reported that both thickness and loca­ are the thickness and stress of the coating, respectively. Since Ef and νf
tion of the interlayer can influence the stress relief [15]. It was also are elastic constants, GS is determined by the thickness and residual
found that a stress gradient is formed nearby the coating/interlayer stress of the coating.
interface by which the residual stress can be gradually decreased [14], The plastic behaviors of Ti and Zr metals have been studied by Reed-
and the relief of stress is dependent on the flow stress of the interlayer Hill et al. [32,33] using the Hollomon's equation [34]. Accordingly, we
[25,26]. Therefore, plastic deformation of the metal interlayer is closely assume that the plastic flow behavior of the metal interlayer can be
related to the stress relief. described by the Hollomon's equation expressed as [34]
It is usually problematic to measure the residual stress of individual
σ = k εn , (2)
layer on a bilayer hard coating; only few studies reported the extent of
stress relief (Δσ%) by introducing a pure metal interlayer. Our previous where σ is the flow stress, ε is the flow strain, k is the strength coefficient
studies [17,18] determined the residual stress in TiN thin films with Ti
and n is the strain hardening exponent of the metal. Since the interlayer
interlayer using cos2αsin2ψ method by X-ray diffraction (XRD) [27]. We in the bilayer specimen is subjected to balanced biaxial stress state, the
found that the residual stress in TiN top layer was significantly relieved
relation of flow stress and strain should be changed to [35].
by more than 50% when Ti interlayer was 150 nm. The results also
qualitatively indicated that stress in the TiN coating can be relieved by a σ = k εn , (3)
sufficiently thick Ti interlayer that is under tensile stress state. However,
the amount of stress relief was not fully accurate because the deviation where σ and ε are the effective stress and strain, respectively. The
of stress measurement by XRD could be up to 30% compared with that relationship between σ and ε and uniaxial stress and strain, σ1 and ε1,
by the wafer curvature method (WCM) [28]. Generally speaking, the can be derived as follows. From the von Mises' yield criterion, σ is given
most reliable nondestructive method for stress measurement on thin as
films is the WCM, by which the overall stress of thin film can be √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
1[ ]
measured with an uncertainty less than 3%. In recent years, the accuracy σ= (σ 1 − σ2 )2 + (σ2 − σ 3 )2 + (σ 3 − σ1 )2 . (4)
2
of stress measurement in TMeN thin films has been greatly improved.
Using the newly developed average X-ray strain (AXS) method com­ From Eq. (4), under balanced biaxial stress, σ 1 = σ 2 and σ 3 = 0, the
bined with the elastic constant obtained from nanoindentation, an effective stress is
advanced technique based on the cos2αsin2ψ method, we can measure
σ = σ1 . (5)
the stress in TMeN thin films with a deviation less than 10% compared
with that by WCM [29,30]. Moreover, the stress measurement for the According to the von Mises' yield criterion, ε is expressed as
individual layer in a bilayer thin film is only viable by the XRD method. [ ]
2( 2 ) 1/2
Using the new technique [29,30], we measured residual stress in dε = dε1 + dε22 + dε23 . (6)
TiZrN/Ti coatings on AISI D2 steel substrate [5,6]. The results showed 3
that as the compressive stress in the top TiZrN layer was higher than - 4 The variation of volume is the sum of the variation of true strain.
GPa, the stress in the Ti interlayer was compressive and up to 3 times of Since volume is constant in plastic deformation, dV = dε1 + dε2 + dε3 =
the yield strength of Ti, about 450 MPa, and the compressive stress was 0, and is rearranged as
also found in the D2 steel substrate at the location near Ti/D2 interface.
Evidently, the plastic deformation of Ti interlayer and D2 substrate is dε1 + dε2 = − dε3 . (7)
involved in the stress relief of TiZrN hard coatings. Therefore, a model Under balanced biaxial stress, the in-plane strain is given as
involving plastic deformation of metal interlayer is needed to explore
the stress relief by the metal interlayer. dε1 = dε2 . (8)
The objective of this study was to evaluate the extent of stress relief Substituting Eq. (8) into Eq. (7), the relation between ε1 and ε3 is
and energy relief efficiency of metal interlayers in bilayer ZrN/Zr and obtained as
ZrN/Ti thin films using an energy balance model based on the concept
that the stored elastic energy in the ZrN coating could be partly relieved 2dε1 = − dε3 . (9)
by the plastic deformation of metal interlayer. In this study, ZrN/Ti and
ZrN/Zr bilayer thin films were chosen as the model systems, because ZrN Substituting Eqs. (8) and (9) into Eq. (6), dε is calculated as dε =
is one of the most popular protective hard coatings owing to its superior { [ ] }1/2
hardness, high corrosion resistance and thermal stability. The metal 2
dε21 + dε21 + ( − 2dε1 )2 = 2dε1 , and the effective strain is
3
interlayers, Zr and Ti, were selected with the consideration of their
different strain hardening behavior. ZrN coatings with different thick­ ε = 2ε1 . (10)
nesses of Ti or Zr interlayers and ZrN/Ti specimens with different stress
levels in ZrN were prepared using unbalanced magnetron sputtering The plastic work of the interlayer due to plastic deformation is given
(UBMS). The overall residual stress of the specimens was determined by by
LCM and the individual layer stress was measured using the AXS com­
bined with nanoindentation method.

2
J.-H. Huang et al.
∫
w= σdε, (11)
where w is the plastic work per unit volume. The upper limit of plastic
deformation can be set at the uniform strain where necking occurs,
where the Considère's criterion ddσε = 2σ is satisfied under balanced biaxial
stress state [35]. By substituting Eq. (3) into the Considère's criterion,
the effective strain can be calculated as
ε = 2n. (12)
From Eq. (10), the flow strain is expressed as
ε1 = n. (13)
Since the bending of a coating specimen is due to the residual stress
in the coating, the residual stress obtained from the laser curvature
method (σLCM) should be consistent with that measured by X-ray
diffraction (σXRD). In other words, the elastic energy in the coating is
fully used in the bending of the entire specimen. By contrast, it was
found that σXRD could not match σLCM for a bilayer specimen with a
metal interlayer [19]. Evidently, the metal interlayer played a role in
stress relief that caused the discrepancy between σXRD and σLCM in the
bilayer specimen. In view of energy balance, the stored elastic energy in
the hard coating is partly consumed by the metal interlayer through
plastic deformation and the rest is transferred to the bending of Si
substrate. However, the stored elastic energy calculated from substrate
bending is not consistent with that calculated from the stress of top hard
coating, indicating that there is another part of energy relief from the
relaxation of substrate bending. Therefore, the energy relief by the
interlayer can be divided into two parts, one is the energy relief in the
coating and the other is the relaxation of substrate bending. In this
study, the coating is ZrN and the metal interlayer is Zr or Ti. The energy
relief in the coating can be defined as
ΔGS,ZrN = GS,ZrN(LCM) − GS,ZrN/metal(XRD) , (14)
where GS,ZrN(LCM) is the stored energy of the monolayer ZrN coating
calculated by Eq. (1), and GS,ZrN/metal(XRD) is the stored energy of the
coating in the bilayer specimen. GS,ZrN/metal(XRD) is calculated by
substituting σXRD into σf in Eq. (1) to separately determine the stored
energy in the coating. The energy relief due to the relaxation of substrate
curvature can be calculated by
ΔGS,Si = GS,ZrN/metal(XRD) − GS,ZrN/metal(LCM) , (15)
where both GS,ZrN/metal(XRD) and GS,ZrN/metal(LCM) are calculated by Eq. (1)
using σXRD and σLCM in the same bilayer specimen, respectively. Thus,
the total relief of stored energy ΔGtot is given as
ΔGtot = ΔGS,ZrN + ΔGS,Si = wi hi (16)
and
∫ ∫
wi hi = hi σ i dεi = 2hi σ i dεi , (17)
where wi is the effective plastic work, hi is the thickness, σi is the flow
stress and εi is the plastic strain of the interlayer.
According to the von Mises' yield criterion, the yield strength under
balanced biaxial stress state is the same as that under uniaxial condition
(Eq. (5)). From Eq. (17), the maximum plastic work of interlayer (Wp,
max) can be calculated by setting εi = n as the upper limit, following the
Considère's criterion, and the result is expressed as
n+1
2kε 2k(n)n+1
Wp,max =
1necking
hi = hi (18)
n+1 n+1
Since the area of the interlayer is the same as that of the coating, the
maximum plastic work that the interlayer can sustain is proportional to
the interlayer thickness.
3
Surface & Coatings Technology 434 (2022) 128224
If the actual work is contributed from the sum of the energy relief in
the coating and the curvature relaxation of the substrate, the efficiency
of total energy relief by the interlayer (ξtot) can be defined as
ΔGtot
ξtot = , (19)
Wp,max
and the contributions by the coating (ηf) and by Si (ηSi) are respectively
defined as
ΔGf
ηf = , (20)
ΔGtot
and
ΔGSi
ηSi = . (21)
ΔGtot
3. Experimental details
ZrN thin film specimens with Ti (ZrN/Ti) and Zr (ZrN/Zr) interlayers
were prepared using UBMS. The substrate material was P-type Si(100)
wafer with dimensions of 15 × 15 × 0.525 mm3. The substrates were
ultrasonically cleaned in acetone and methanol, progressively, each for
5 min, and dried by blowing nitrogen gas. Then, the substrates were
immediately placed into the deposition chamber that was evacuated
down to a base pressure of 6.7 × 10− 4 Pa (5.0 × 10− 6 Torr) to avoid the
contamination during deposition. Each batch of deposition contained
twelve pieces of substrates.
ZrN/Ti and ZrN/Zr specimens were deposited by UBMS. The target
materials were 2-in Ti target (99.995% in purity) and Zr target (99.9% in
purity), and the distance from target to substrate was 10 cm. Before
deposition, the substrates were pre-sputtered by Ar ions at a negative
bias of 800 V with Ar flow rate of 25 sccm for 5 min to remove the native
oxide on the surface. The substrate rotational speed was set at 18 rpm.
The working pressure was controlled at 2.5 × 10− 1 Pa (1.9 × 10− 3 Torr)
by adjusting the gate valve of turbo molecular pump and flow rate of Ar
gas was reduced to 16 sccm. Two kinds of interlayers, Ti and Zr, were
deposited with substrate bias voltages of − 60 and − 70 V, respectively,
and the thickness of interlayers was controlled at 100, 200 and 300 nm
by adjusting the deposition durations. Afterwards, the top ZrN thin film
was deposited by introducing N2 reactive gas with a flow rate of 1.3
sccm. The residual stress in ZrN of the ZrN/Ti specimens was controlled
by applying different substrate bias voltages, ranging from − 48 to − 63
V. For the ZrN/Zr specimens, a constant negative substrate bias of 70 V
was applied. The deposition temperatures for ZrN/Ti and ZrN/Zr spec­
imens were 300 and 350 ◦ C, respectively.
The chemical compositions of the specimens were determined by an
X-ray photoelectron spectroscope (XPS) with an X-ray source of Al Kα (λ
= 1486.6 eV) operated at 15 kV. The deconvolution and fitting of the
multiplex spectra were conducted using a computer program XPSPEAK
4.1, where the background was subtracted by the Shirley's method [36].
The crystal structure and preferred orientation of the specimens were
determined by XRD and glancing incidence XRD (GIXRD). The X-ray
source was Cu Kα1 with λ = 1.5406 Å operated at 40 kV × 35 mA. The
scan rate was 2◦ /min with step size of 0.02◦ for both XRD and GIXRD.
The ranges of 2θ scan for XRD and GIXRD were 20–65◦ and 20–100◦ ,
respectively. The XRD pattern was used to identify the crystal structure
and determine the preferred orientation that is represented by texture
coefficient (TC) defined as TC = ∑II(hkl) , where I is the integrated in­
hkl
tensity of the corresponding diffraction peak (hkl). The grain size of the
film was estimated by the Scherrer equation [37]. The X-ray incident
angle of GIXRD was 2◦ , and the diffraction pattern was used for phase
identification and to calculate the lattice parameters of the specimens.
The cross-sectional microstructure and surface morphology of the
specimens were observed using field-emission gun scanning electron
microscopy (FEG-SEM). The film thickness was measured from the cross-
J.-H. Huang et al. Surface & Coatings Technology 434 (2022) 128224

sectional image. The film thickness was confirmed by the compositional Table 1
depth profiles measured using Auger electron spectroscopy (AES). The Summary of film thickness, composition, grain size, lattice parameter, and
relative intensity of elements was calibrated using the XPS composi­ surface roughness of ZrN and ZrN/Ti, and ZrN/Zr thin films.
tional information of the specimens. The sputtering yield was calculated Specimen Thickness Bias N/Zr Grain Lattice Roughness
by dividing film thickness, measured from the cross-sectional SEM no. ZrN/ (-V) ratio size parameter (nm)
image, with sputtering time. metal ZrN (Å)
(nm) (111)
The hardness and Young's modulus of the specimens were deter­
(nm)
mined by a nanoindenter equipped with a Berkovich diamond indenter
ZrN/Ti
head. The indentation depth was kept less than one tenth of the entire
Z00 810/0 48 0.9 20 4.559 1.6
film thickness by applying load ranging from 3000 to 4500 μN to avoid Z01 802/0 53 0.9 20 4.556 1.8
the substrate effect. The hardness and Young's modulus (Ef) of the thin Z02 814/0 58 0.9 20 4.553 1.4
film was measured following the Oliver-Pharr method [38]. The Pois­ Z03 766/0 63 0.9 20 4.557 1.1
son's ratio of ZrN (ν = 0.186) was adopted from literature data [39]. For Z02 814/0 58 0.9 20 4.553 1.4
Z12 918/101 58 1.0 17 4.561 4.9
each sample, ten measurements were performed and the average was Z22 906/201 58 0.9 17 4.563 7.2
reported. The uncertainty of the measurement was within 10%. An Z32 916/295 58 1.0 19 4.563 8.3
atomic force microscope (AFM) operated at contact mode was used to Z20 863/198 48 0.9 18 4.568 7.8
observe the surface morphology and determine the roughness. The scan Z21 861/200 53 0.9 18 4.563 8.3
Z22 906/201 58 0.9 17 4.563 7.2
rate and scan area of AFM were 4 Hz and 2 × 2 μm2, respectively.
Z23 836/202 63 0.9 18 4.560 8.7
The residual stress of the entire specimen for both monolayer and
bilayer thin films was determined by LCM, where the difference in the ZrN/Zr
Zr0 996/0 70 1.0 18 4.577 1.7
characteristic curvature of the substrate before and after film deposition
Zr1 1040/ 70 1.0 21 4.579 3.0
was measured, and the stress was calculated by modified Stoney's 101
equation [40]. Stress of the specimen was measured at three rotational Zr2 1160/ 70 1.0 22 4.578 3.8
angles 0◦ , 45◦ and 90◦ , and twelve scanning paths with interval of 0.05 228
Zr3 915/293 70 0.9 22 4.576 3.6
mm was conducted on the sample surface. The reported residual stress
was the average of the measurements on eight specimens in the same
batch.
The average X-ray strain (AXS) combining with nanoindentation Table 2
method [29,30] was employed to measure the residual stress of the in­ Summary of properties, including residual stress, hardness, and Young's
dividual layer of specimens using a 4-circle diffractometer with psi- modulus of ZrN and ZrN/Ti, and ZrN/Zr thin films.
goniometer. The X-ray source was CuKα1 with wavelength λ = 1.5406 Specimen Optical X-ray residual stress Hardness Young's
Å operated at 40 kV × 35 mA. The diffraction peaks of ZrN (220) at 2θ = no. stress of ZrN (GPa) modulus
(GPa)
56.98◦ and Ti (0002) at 2θ = 38.42◦ were selected for the measurements
σLCM σXRD,ZrN
(GPa) (GPa)
of residual stresses in the corresponding layer. The X-ray incident angle
Z00 − 2.87 ± 25.5 311.5 ± 9.1
was chosen according to the X-ray penetration depth that could cover – ±
0.12 1.2
the entire thickness of thin film. The X-ray incident angle for all speci­ Z01 − 3.02 ± − 3.39 ± 0.09 26.8 ± 319.9 ± 8.4
mens was 6◦ , and the strain of ZrN was measured by cos2αsin2ψ method 0.05 1.4
[27] with five azimuthal angles (ϕ), 0◦ , 45◦ , 90◦ , 135◦ , and 180◦ , and Z02 − 3.51 ± − 3.87 ± 0.09 29.4 ± 328.9 ± 6.2
nine tilting angles (ψ), 0◦ , ±23◦ , ±33◦ , ±42◦ , and ±50◦ . The strain 0.14 1.2
Z03 − 3.94 ± − 4.21 ± 0.08 28.6 337.5 ± 8.7
measurement of Ti interlayer was conducted with seven azimuthal an­
±
0.09 0.9
gles (ϕ), 0◦ , 30◦ , 60◦ , 90◦ , 120◦ , 150◦ , and 180◦ , and nine tilting angles Z02 − 3.51 ± − 3.87 ± 0.09 29.4 ± 328.9 ± 6.2
(ψ) 0◦ , ±23◦ , ±33◦ , ±42◦ , ±50◦ . 0.14 1.2
Z12 − 1.92 ± − 2.65 ± 0.09 26.6 ± 320.6 ± 18.3
0.07 1.5
4. Results
Z22 − 1.62 ± − 2.18 ± 0.08 24.8 ± 329.8 ± 26.9
0.07 2.9
In this study, the interlayer thickness and negative substrate bias of Z32 − 1.51 ± − 2.66 ± 0.05 25.3 ± 365.2 ± 24.3
the bilayer specimens were chosen as the experimental variables. 0.07 2.6
Accordingly, the designation of the specimens was derived from the Z20 − 0.73 ± − 1.15 ± 0.10 24.5 ± 348.4 ± 30.3
0.15 2.0
experimental variables, as listed in Table 1. The first digit ranging from Z21 − 1.29 ± − 1.94 ± 0.08 25.7 ± 333.9 ± 25.6
0 to 3 denotes the interlayer thickness corresponding to 0, 100, 200, and 0.12 2.8
300 nm. The second digit ranging from 0 to 3 represents the applied Z22 − 1.62 ± − 2.18 ± 0.08 24.8 ± 329.8 ± 26.9
negative substrate bias corresponding to − 48, − 53, − 58, and − 63 V. 0.07 2.9
Z23 − 2.49 ± − 3.97 ± 0.07 26.8 359.7 ± 13.9
There are three series of ZrN/Ti specimens, including one series of ±
0.11 1.5
monolayer ZrN and two series of bilayer specimens with different Zr0 − 4.63 ± − 5.46 ± 0.10 27.6 ± 338.7 ± 7.0
interlayer thicknesses and deposited at different substrate bias voltages, 0.08 0.9
abbreviated as Z0X, ZX2, and Z2X, respectively. Only one series of ZrN/ Zr1 − 4.09 ± − 5.03 ± 0.07 29.7 ± 354.1 ± 11.1
Zr specimens with different Zr interlayer thicknesses were prepared, 0.03 1.2
Zr2 − 3.86 ± − 4.63 ± 0.09 30.2 359.4 ± 22.9
which is designated as ZrX where X ranging from 0 to 3 denotes the same
±
0.06 2.8
interlayer thickness as ZrN/Ti specimens. The experimental results are Zr3 − 3.88 ± − 4.87 ± 0.07 28.7 ± 338.3 ± 15.5
summarized in Tables 1 to 3. 0.06 2.3
The chemical compositions of ZrN thin films and bilayer specimens
with Ti or Zr interlayers are listed in Table 1. The results show that the
XRD patterns of all series specimens are depicted in Fig. 2. Some
N/Zr ratio ranges from 0.9 to 1.0 for all specimens. Fig. 1 reveals the
apparent diffraction peaks are observed, including ZrN (111), ZrN (200),
XRD patterns of Ti and Zr thin films with different thicknesses, 100, 200,
and 300 nm, indicating that there is no preferred orientation in the Ti ZrN (220), Ti (0002), Ti (1011), and Zr (0002), which also confirm the
thin films, while the Zr thin films have (0002) preferred orientation. The existence of Ti interlayer in the ZrN/Ti and Zr interlayer in the ZrN/Zr

4
J.-H. Huang et al. Surface & Coatings Technology 434 (2022) 128224

Table 3 layer by introducing a Ti interlayer. For the ZrN/Zr (ZrX series) speci­
Summary of relief of residual stress. The extent of stress relief (Δσ%) are referred mens, as shown in Fig. 2(d), the ZrN top layers all show strong (111)
as: (1) between monolayer ZrN (σLCM,ZrN or σXRD,ZrN) and ZrN in bilayer spec­ texture with or without Zr interlayer. The lattice parameter of the
imen (σXRD,ZrN) and (2) between monolayer ZrN (σLCM,ZrN) and overall bilayer specimens was obtained from GIXRD patterns and listed in Table 1. The
σXRD,ZrN − σLCM,ZrN
ZrN (σLCM), where (1) ΔσLCM-XRD% = , and (2) ΔσLCM-LCM% = lattice parameters range from 4.553 to 4.579 Å, which mostly match the
σLCM,ZrN
σLCM − σLCM,ZrN database of International Centre for Diffraction Data (ICDD) [41].
.
σLCM,ZrN The microstructure of the specimens was examined by SEM cross-
sectional images. The film thickness of the specimens was also
Specimen no. ΔσLCM-XRD% ΔσLCM-XRD ΔσLCM-LCM% ΔσLCM-LCM (GPa)
(%) (GPa) (%) measured from the SEM images, as listed in Table 1. Fig. 4 shows the
representative cross-sectional SEM images of the ZrN, ZrN/Ti and ZrN/
Z12 24.5 0.86 45.3 1.59
Z22 37.9 1.33 53.8 1.89 Zr specimens. The monolayer ZrN possesses typical zone-T columnar
Z32 24.2 0.85 57.0 2.00 structure, as shown in Figs. 4(a) and (e). For the ZrN/Ti bilayer speci­
Z20 59.9 1.72 74.6 2.14 mens, Fig. 4(b, c, d), the SEM images reveal a distinct Ti interlayer be­
Z21 35.8 1.08 57.3 1.73 tween top layer and substrate, the existence of Ti interlayer is confirmed
Z22 37.9 1.33 53.8 1.89
again. In addition, the columnar width of the specimens increases by
Z23 0a 0a 36.8 1.45
Zr1 7.9b 0.43b 11.7 0.54 introducing Ti interlayer, and the bilayer specimens have less dense
Zr2 15.2b 0.83b 16.6 0.77 structure than the monolayer ZrN specimens. By contrast, the ZrN/Zr
Zr3 10.8b 0.59b 16.2 0.75 specimens show a better interface between ZrN and Zr interlayer
a
Within the uncertainty of measurement. compared with ZrN/Ti specimens, as shown in Fig. 4(f, g, h). Similarly,
b
Δσ was calculated by σXRD,ZrN-σXRD, ZrN/Zr, the difference in stress of ZrN the columnar width of ZrN also increases by adding the Zr interlayer.
between monolayer and bilayer specimens. The AES compositional depth profiles of Z12 specimen is shown in
Fig. 5. A few different regions are observed, including the ZrN top layer,
mixing layer, Ti interlayer, and the substrate. From the AES data, the
presence of Ti interlayer is confirmed and the thickness of Ti interlayer is
about 100 nm that is consistent with the thickness measured from SEM
image. Furthermore, the existence of a mixing layer, about 50 nm, as­
sures the interface quality between ZrN and Ti interlayer such that the
energy in ZrN can soundly transfer into the interlayer.
The surface morphology and surface roughness are observed by
AFM. The root mean square roughness numbers (Rrms) of the specimens
are listed in Table 1. The results show that the values of Rrms of mono­
layer Zr0 and Z0X-series specimens are less than 2 nm. However, the
roughness of ZrN deposited on Ti interlayer increases with interlayer
thickness, ranging from 4.9 to 8.7 nm, which could be related to the
roughness of the Ti interlayer. By contrast, the roughness increase of the
ZrN specimen by introducing Zr interlayer is less distinct, ranging from
3.0 to 3.8 nm.
The hardness and Young's modulus were determined by nano­
indentation and the results are listed in Table 2. The results indicate that
the hardness of all specimens is above 24.5 GPa, which is comparable
with the literature data of ZrN thin films. The hardness of the specimens
slightly decreases by introducing a Ti interlayer. On the other hand, the
hardness of ZrN increases by adding a Zr interlayer. The Young's
modulus of the specimens ranges from 311 to 365 GPa. The substrate
effect can be neglected because the thickness of all specimens is larger
than 700 nm [29]. The average value of Young's modulus of ZrN for Z0X,
ZX2 and Z2X specimens is 334.5 GPa and that for ZrX specimens is
347.6 GPa, which are consistent with literature data [9,39].
The residual stress in the specimens was measured by LCM and AXS
accompanying with nanoindentation method. The results of the residual
stress in Z0X-, ZX2-, Z2X- and ZrX-series of specimens are listed in
Table 2. In this study, negative substrate bias voltage was used to control
the magnitude of residual stress of the ZrN thin films. The substrate bias
voltage will attract Ar+ and N2+ ions to impinge the adatoms on sub­
strate surface, which may generate trapping Ar atoms or metal atoms in
the interstitial sites, thereby leading to compressive residual stress,
which is so called ion peening effect [42–44]. Due to the ion peening
effect, a higher negative substrate bias results in a higher stress in the
ZrN films. The effect of negative substrate bias on residual stress in ZrN
Fig. 1. XRD patterns of (a) Ti and (b) Zr thin films with different thickness. is shown in Fig. 6. The results indicate that residual stress in the ZrN
monolayer thin film almost linearly increases with substrate bias voltage
specimens. The grain size of the ZrN top layer ranges from 17 to 22 nm ranging from − 48 to − 63 V, suggesting that the residual stress in ZrN is
estimated by the Scherrer equation, as listed in Table 1, indicating that effectively controlled by changing substrate bias voltage.
the thin films have nanocrystalline structure. The effect of Ti interlayer To study the effects of Zr and Ti interlayers on stress relief in the
on the preferred orientation of ZrN top layer is depicted in Fig. 3. The bilayer specimens, the residual stress is divided into two categories, the
results show no significant effect on texture coefficient of the ZrN top overall stress in the bilayer specimens (σLCM), and the stress in ZrN for

5
J.-H. Huang et al.
Fig. 2. XRD patterns for the (a) Z0X, (b) ZX2, (c) Z2X, and (d) ZrX series specimens.
monolayer and bilayer specimens (σXRD, ZrN). The stress relief from ZrN
top layer due to different Zr and Ti interlayer thickness and substrate
bias are listed in Table 3. Fig. 7 shows the residual stress in ZrN (σXRD,
ZrN) and overall specimen (σLCM) with respect to interlayer thickness and
substrate bias for ZrX-, Z0X-, ZX2-, and Z2X- series of specimens. It can
be found that σLCM is relieved with increasing interlayer thickness, as
shown in Fig. 7(a, b), where the stress relief by Ti interlayer is more
significant than that by Zr. Fig. 7(c) shows a consistent trend that stress
increases with negative bias in both monolayer and bilayer specimens.
In addition, Fig. 7(c) indicates that the stress is progressively relieved by
comparing stress in the corresponding specimens of monolayer ZrN and
overall ZrN/Ti bilayer (σLCM). On the other hand, the stress in ZrN layer
(σXRD,ZrN) is not always relieved by the interlayer; especially, at high
stress conditions, specimens Z23 and Z32, the extent of stress relief
decreases, as shown in Fig. 7(b, c).
The extents of stress relief (Δσ%) for the bilayer specimens are listed
in Table 3. It is interesting to find that the extent of stress relief by Zr
interlayer (ΔσLCM-LCM%) is much lower than that by Ti interlayer. Δσ%
with respect to different interlayer thickness for ZrN/Zr and ZrN/Ti
bilayer specimens are shown in Fig. 8(a, b), respectively. For Zr inter­
layer (Fig. 8(a)), the extent of stress relief in overall specimen (ΔσLCM-
LCM%) slightly increases with increasing Zr interlayer thickness and
levels off at 16% when the thickness increases to 200 nm and above. By
contrast, for Ti interlayer (Fig. 8(b)), ΔσLCM-LCM% almost linearly in­
creases with increasing Ti interlayer thickness. The extent of stress relief
in ZrN for both Zr interlayer (ΔσXRD-XRD%) and Ti interlayer (ΔσLCM-
XRD%) increases with interlayer thickness from 100 to 200 nm, but de­
creases at interlayer thickness of 300 nm. Note that σXRD,ZrN of specimen
Zr0 was chosen to be the reference in calculating the stress relief in ZrN/
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Surface & Coatings Technology 434 (2022) 128224
Zr specimens, because the significant deviation in the stress measured by
XRD and LCM. The extents of stress relief with respective to negative
substrate bias (Z2X-series) are shown in Fig. 8(c), where ΔσLCM-LCM%
decreases with increasing substrate bias. ΔσLCM-XRD% shows a similar
trend except for specimen Z22 that has nearly the same amount of stress
relief as Z21. However, the difference between σLCM of bilayer specimen
and σLCM,ZrN of monolayer specimen only reveals the stress relief of
overall specimen by introducing the metal interlayer, but the stress relief
contributions of ZrN and Si substrate cannot be separated by the stress
analysis.
5. Discussion
In this study, the proposed physical model considers plastic defor­
mation, in addition to stored elastic energy, to account for the stress
relief by the metal interlayer in a bilayer thin film architecture. The
model is based on energy balance, instead of stress balance, to explore
the issue of energy relief in a bilayer coating with pure metal interlayer,
where the total relief of stored elastic energy including both coating and
substrate is assumed to be converted to plastic work by the interlayer.
Furthermore, the stress in the hard coating of bilayer specimen is
directly measured using the AXS method and is compared with the stress
of the hard coating in the corresponding monolayer specimens, by which
the actual relief of stress and stored energy in the coating can be ob­
tained. However, the contribution of stress or energy relief from the
substrate needs to be further explored.
It is noted that the stress in the hard coatings of bilayer specimens
(σXRD,ZrN) is always higher than the overall stress measured by LCM
(σLCM), as shown in Fig. 7. The stress difference between σXRD,ZrN and
J.-H. Huang et al. Surface & Coatings Technology 434 (2022) 128224

ΔGS,Si) is converted into plastic work, the efficiency of energy relief (ξtot)
can be given as (ΔGS,ZrN + ΔGS,Si)/Wp,max. The data of ξtot for ZX2, Z2X
and ZrX specimens are listed in Table 4. ξtot with respect to interlayer
thickness and substrate bias voltage are shown in Fig. 9(a, b) and (c),
respectively. The results indicate that ξtot decreases with the interlayer
thickness and ξtot of Zr interlayer is slightly less than that of Ti interlayer,
ranging from 79.0 to 33.2% for Zr interlayer and 83.1 to 35.4% for Ti
interlayer (Fig. 9(a)). By contrast, the efficiency shows a less distinct
trend with the substrate bias voltage (or the stress in ZrN), ranging from
39.1 to 48.8% (Fig. 9(b)).
The total energy relief by the metal interlayer is divided into two
parts corresponding to the two energy relief mechanisms. One is the
energy relief in ZrN coating and the other is the energy relief due to the
curvature relaxation in the Si substrate. The contributions of energy
relief by ZrN and Si, ηZrN and ηSi, are calculated by Eqs. (20) and (21), as
listed in Table 4. It is found that Zr interlayer shows a different behavior
in energy relief compared with Ti interlayer, as shown in Fig. 10(a, b).
For the ZrN/Zr specimens, the energy relief is mainly due to the cur­
vature relaxation of Si substrate (Fig. 10(a)), where the ηSi gradually
decreases with increasing Zr interlayer thickness and reaches 50% at
300 nm. For the ZrN/Ti specimens (Fig. 10(b)), ηZrN shows a maximum
at 200 nm interlayer thickness, and about 50% at both 100 and 300 nm
thickness. By contrast, Fig. 10(c) indicates that ηZrN decreases with
increasing stress from − 1.15 to − 1.94 GPa in the hard coating while
slightly increases as the stress further increases to − 2.18 GPa, and
abruptly decreases from 74.9 to 0% as the stress in ZrN is close to − 4
GPa.
Comparing the results of extent of stress relief (Fig. 8) with that of
efficiency of energy relief (Fig. 9), it can be found that the latter is a
better index in evaluating the effectiveness of metal interlayer. Fig. 8(b,
c) indicates that the stress relief in ZrN coating may have different trend
compared with that in the overall specimen, because the contribution of
stress relaxation in Si substrate cannot be properly evaluated. By
contrast, the energy relief efficiency includes contributions from both
Fig. 3. The variation of texture coefficients with (a) interlayer thickness and (b)
coating and substrate, which shows a clear picture on consumption of
negative substrate bias. The open symbol is monolayer ZrN and solid symbol is
the capability of metal interlayer on energy or stress relief. In addition,
ZrN/Ti bilayer specimens.
the contributions to the energy relief from coating and substrate can be
separately evaluated, as shown in Fig. 10, which further clarifies the
σLCM implies that there is a stress relief other than that in the ZrN
stress relief mechanism in the metal interlayer. Therefore, it may be not
coating. Since the stress in ZrN coating is measured by XRD, the addi­
a reliable approach on evaluating the effectiveness of metal interlayer in
tional stress relief of the overall specimen must be derived from the
the bilayer specimen by only using LCM to measure the overall stress of
curvature relaxation of Si substrate, where the energy relief is also
the specimen. Additional XRD methods, such as the AXS method, are
through converting the elastic energy to the plastic work by the metal
suggested to accurately measure the stress in the coating. From the stress
interlayers. As a result, there are two stress relief mechanisms in the
data respectively measured by the two methods on the monolayer and
bilayer specimen, one is from ZrN coating by stretching the metal
bilayer specimens, the analysis of energy relief can be carried out, and
interlayer to relieve the compressive stress, and the other is from the
the efficacy of the interlayer can be properly assessed.
curvature relaxation of Si substrate by compressing the metal interlayer,
Closely examining the results depicted in Figs. 9 and 10, there are
and both mechanisms transfer stored elastic energy into the metal
some interesting findings. By increasing the interlayer thickness, the
interlayer. Since the stress state and plastic deformation are complicated
capability of energy relief is supposed to be increased according to Eq.
in the interlayer, it is difficult to separate the stress relief contributions
(16); however, the energy relief efficiency does not increase but de­
of ZrN and Si substrate by the stress analysis. Alternatively, the energy
creases, as shown in Fig. 9(a), indicating that the amount of stored en­
balance model can provide a convenient approach to estimate the in­
ergy that can be converted to plastic work of the metal interlayer may be
dividual contributions of ZrN and Si in energy relief.
limited to a certain extent. The reason is not fully understood and need
The relief of stored energy in ZrN (ΔGS,ZrN) can be calculated from
further exploration. Fig. 9(a) indicates that there is an optimum inter­
the difference in GS,ZrN between bilayer and monolayer specimens, GS,
layer thickness, by which the energy relief efficiency or the consumption
ZrN(LCM) - GS,ZrN/Ti(XRD) or GS,ZrN(XRD) - GS,ZrN/Zr(XRD). In this study, GS,ZrN
of the capability of Ti or Zr interlayer can reach a high extent, 83.1% and
(LCM), GS,ZrN(XRD), GS,ZrN/Ti(XRD) and GS,ZrN/Zr(XRD) were separately
79.0% for Ti and Zr interlayers, respectively. This result suggests that
measured and calculated to attain ΔGS,ZrN, where Young's modulus of
the high stress in hard coatings cannot be relieved by solely increasing
the corresponding specimen was used in the calculation. The energy due
the interlayer thickness in practical applications. On the other hand, the
to the substrate relaxation (ΔGS,Si) can be obtained from the difference
energy relief efficiency seems to be less dependent on the stress level in
in stored energy in ZrN coating (GS,ZrN/Ti(XRD)) and that in overall
the hard coating. With 37% increase of stress in the hard coating from
specimen (GS,ZrN/Ti(LCM)). The results of ΔGS,ZrN and ΔGS,Si are listed in
− 2.87 to − 3.94 GPa, the variation of energy relief efficiency is only
Table 4, where the values of total energy relief (ΔGS,ZrN + ΔGS,Si) for all
9.7%. In particular, the energy relief efficiency in specimen Z23 is
specimens are less than the maximum plastic work of interlayer (Wp,
mostly contributed from Si substrate, the negative ΔGS,ZrN denotes that
max), indicating that using the Ti or Zr interlayers is effective in relieving
the elastic energy in ZrN does not relieve but increases (Table 4). This
the stress in the bilayer coatings. Since the total energy relief (ΔGS,ZrN +
indicates that the high compressive stress in ZrN becomes a restriction of

7
J.-H. Huang et al.
(a) Z02
(c) Z22
(e) Zr0
(g) Zr2
Fig. 4. Cross-sectional microstructure of (a) Z02, (b) Z12, (c) Z22, (d) Z32, (e) Zr0, (f) Zr1, (g) Zr2, and (h) Zr3 specimens.
energy relief in the ZrN coating. By contrast, the energy relief did occur
by the curvature relaxation of Si substrate, and converting to the plastic
work of Ti interlayer. Therefore, the total energy relief is only from ΔGS,
Si, while no contribution is from ΔGS,ZrN.
Our previous studies [5,6] reported that the wear resistance of hard
coatings is related to the stored elastic energy in the coatings. The wear
resistance of TiZrN coatings increases with decreasing stored elastic
energy in the coatings. We also found that the improvement of wear
resistance and adhesive strength was limited by using Ti interlayer,
when the residual stress in the hard coatings was higher than − 4 GPa.
The stresses in specimens Z03 and Z23 are close to − 4 GPa, and the
energy or stress in the coating cannot be relieved by the Ti interlayer,
thereby the stored energy in the hard coating remaining at high level,
which may explain the limited improvement of the tribological prop­
erties of highly stressed TiZrN hard coatings by using Ti interlayer.
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Surface & Coatings Technology 434 (2022) 128224
(b) Z12
(d) Z32
(f) Zr1
(h) Zr3
500 nm
The difference in energy relief efficiency (ξtot) between Zr and Ti
interlayers is worth further exploration. Although ξtot shows similar
trends with interlayer thickness for Zr and Ti (Fig. 9(a)), the contribu­
tions of energy relief by ZrN and Si, ηZrN and ηSi are significantly
different, as shown in Fig. 10(a, b). The difference in ηZrN and ηSi can be
attributed to the different plastic behavior of Ti and Zr interlayers. The
plastic behavior of metal interlayer under balanced biaxial stress state
can be described by Eq. (3), σ = kεn . As mentioned, the maximum plastic
work per unit area (Wp,max) absorbed by the metal interlayer can be
calculated by Eq. (18), Wp,max = 2k(n)
n+1
n+1 hi , where hi is the thickness of
metal interlayer. Therefore, Wp,max at fixed thickness depends on the
strain hardening coefficient (n) and the strength coefficient (k). The n
values of Ti and Zr metals are 0.12 [45] and 0.11 [46], respectively,
which is insufficient to cause a substantial effect on energy relief. The
major difference of Ti and Zr metals lies in k values which are 690 MPa
J.-H. Huang et al. Surface & Coatings Technology 434 (2022) 128224

Ti Interlayer
100 Mixing Layer Substrate

ZrN Top Layer

Si
80
Atomic Percentage (%)

O Ti

Zr
60

40 N

20

0
0 200 400 600 800 1000
Depth (nm)

Fig. 5. AES compositional depth profiles of Z12 specimen.

4.5
Compressive Stress (GPa)

4.0

3.5

3.0

2.5
48 53 58 63
Negative Bias Voltage (-V)

Fig. 6. The effect of substrate bias on residual stress of ZrN thin films.

[45] and 1500 MPa [46], respectively, where k of Zr is much higher than
that of Ti, and thus Wp,max of Zr is expected to be larger than that of Ti,
according to Eq. (18). However, the results show that ξtot of Ti interlayer
is 4% higher than that of Zr interlayer (Table 4). From Eq. (3), it is
known that the metal with a higher k needs higher flow stress to reach
the same plastic strain, suggesting that the deformation of Zr metal is
more difficult. As a result, less energy in the ZrN coating can be relieved
by the Zr interlayer and the remaining energy is transferred to the
bending of Si substrate. Consequently, ηZrN is merely 34.7% when the
thickness of Zr interlayer is 100 nm (Fig. 10(a)), where the energy relief
mainly comes from the curvature relaxation of Si substrate by the Zr
interlayer. Due to the difficulty in deformation, a higher ηZrN can only be
achieved through the increase of Zr interlayer thickness, but ηZrN is still
below 50% even though the thickness of Zr reaches 300 nm. By contrast,
k of Ti is lower and the deformation of Ti is easier than Zr, resulting in a
higher ξtot (Fig. 9(a)). The ηZrN values of Ti interlayers, ranging from 100
to 300 nm, are all above 50% (Fig. 10(b)), indicating that Ti interlayer
can effectively relieve the energy in ZrN coating. Thus, in selecting a
metal interlayer, we should consider not only the capacity of energy
absorption (Wp,max) but also the malleability (k) of the metal.
In the energy balance model, it is assumed that the plastic flow
behavior of the metal interlayers can be described by the Hollomon's
equation, which follows the previous studies by Reed-Hill et al. [32,33].
Fig. 7. The variation of residual stress in ZrN with (a) Zr interlayer thickness,
(b) Ti interlayer thickness, and (c) negative substrate bias for all specimens.
The Hollomon's equation is an empirical relationship, where the
isotropic behavior of metals is assumed. However, the Zr interlayer has a
strong fiber texture at 〈0002〉 direction (Fig. 1(b)), which should be
further considered. It is known that for a thin film with fiber texture, the
planes in the azimuthal direction are randomly distributed; in other
words, the azimuthal direction shows isotropic behavior. In addition,
the metal interlayers, with thickness ranging from 100 to 300 nm, are
under balanced biaxial stress. Since there is no stress applied at the
textured direction, it is reasonable to assume that the deformation of Zr
interlayer is isotropic.
In summary, the proposed energy balance model can be used to
evaluate the effectiveness of the interlayer. In the proposed model, the

9
J.-H. Huang et al. Surface & Coatings Technology 434 (2022) 128224

Table 4
Summary of energy relief and efficiency of energy relief for ZX2-, Z2X-, and ZrX-
series specimens, where ΔGS, ZrN = GS,ZrN(LCM) - GS,ZrN/Ti(XRD) or ΔGS,ZrN = GS,ZrN
(XRD) - GS,ZrN/Zr(XRD), ΔGS,Si = GS,ZrN/Ti(XRD)-GS,ZrN/Ti(LCM) or ΔGS,Si = GS,ZrN/Zr
(XRD)-GS,ZrN/Zr(LCM), and ξtot = (ΔGS,ZrN + ΔGS,Si) / Wp,max.

Specimen no. Wp,max ΔGS,ZrN ΔGS,Si ξtot ηZrN ηSi

(J/m2) (J/m2) (J/m2) (%) (%) (%)

Z12 11.6 5.0 4.6 83.1 52.1 47.9

Z22 23.0 8.4 2.8 48.8 74.9 25.1
Z32 33.8 6.2 5.8 35.4 51.4 48.6
Z20 22.7 8.8 0.9 42.7 90.3 9.7
Z21 22.9 6.4 2.6 39.1 70.9 29.1
Z22 23.0 8.4 2.8 48.8 74.9 25.1
Z23 23.2 − 0.7a 10.7 46.3 0.0 100.0
Zr1 23.6 6.4 12.2 79.0 34.7 65.3
Zr2 53.2 8.9 10.2 35.9 46.7 53.3
Zr3 68.3 11.4 11.3 33.2 50.1 49.9
a
Negative sign indicates the increase of stored energy in the ZrN coating.

Fig. 8. The extent of residual stress relief with respect to (a) Zr interlayer
thickness for ZrX series specimens, (b) Ti interlayer thickness for ZX2 series Fig. 9. Efficiency of energy relief (ξtot) with respect to (a) interlayer thickness,
specimens and (c) negative substrate bias for Z2X series specimens. and (b) substrate bias.

stress of the hard coating in the bilayer specimen should be individually application of the model is feasible and convenient.
measured by XRD, the overall stress of the specimen is determined by
LCM, and the nanoindentation is used to measure the elastic modulus of 6. Conclusions
the hard coating. The constants in the plastic flow curve can be adopted
from literature data or determined experimentally. Accordingly, all the In this study, ZrN/Zr and ZrN/Ti bilayer thin films with different
required parameters are measurable and available, ensuring the

10
J.-H. Huang et al.
Fig. 10. Contributions of energy relief from ZrN and Si substrate with respect
to (a) Zr interlayer thickness for ZrX series specimens, (b) Ti interlayer thick­
ness for ZX2 series specimens and (c) negative substrate bias for Z2X se­
ries specimens.
interlayer thickness were deposited on Si substrate by unbalanced
magnetron sputtering, where ZrN/Ti specimens were also prepared at
different negative substrate bias voltages. The residual stress in speci­
mens was measured by laser curvature method and average X-ray strain
combined with nanoindentation method. An energy balance model is
proposed to evaluate the energy relief efficiency (ξtot) by the Ti and Zr
interlayers. The contributions of energy relief by the metal interlayers
from the ZrN coatings (ηZrN) and curvature relaxation of Si substrate
(ηSi) can be individually assessed.
1. Experimental results show that the extent of stress relief (Δσ%) of the
entire specimen, ranging from 45.3 to 57.0%, increases with Ti
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Surface & Coatings Technology 434 (2022) 128224
interlayer thickness, while decreases with increasing stress of top
ZrN layer, ranging from 74.6 to 36.8%.
2. The model analysis shows that ξtot decreases by increasing Zr or Ti
interlayer thickness, where the energy relief is mainly from ηSi for
ZrN/Zr specimens, while ηZrN is the major contribution for ZrN/Ti
specimens. There is an optimum interlayer thickness about 100 nm,
by which ξtot can reach up to 79.0 and 83.1% for Zr and Ti in­
terlayers, respectively. For the specimens deposited at different
substrate bias voltages ranging from − 48 to − 63 V, the variation of
energy relief efficiency is irregular and less distinct, ranging from
39.1 to 48.8%.
3. The results indicate that the energy relief by the Ti interlayer is
mostly from the coatings (ηZrN), except for the specimen with stress
in the ZrN coating close to − 4 GPa, where the energy relief is mainly
due to ηSi. For the ZrN/Zr specimens, the energy relief is mainly due
to ηSi, until the interlayer thickness increases to 300 nm where the
energy in ZrN coating and Si substrate are equally relieved by the Zr
interlayer.
4. Although ξtot can serve as a better index in evaluating the effec­
tiveness of the interlayers compared with Δσ%, the separate assess­
ment of ηZrN and ηSi by the model analysis are crucial, which can
reveal the actual energy relief in the hard coating. It is found that
ηZrN and ηSi are related to the strength coefficient (k) of the inter­
layer. Accordingly, in selecting a metal interlayer, we should
consider not only the capacity of energy absorption (Wp,max) but also
the malleability (k) of the metal.
CRediT authorship contribution statement
Jia-Hong Huang: Conceptualization, Supervision, Writing- Original
draft preparation and Editing, Manuscript revision, Response to re­
viewers, Funding acquisition, Project administration.
Ting-Wei Zheng: Methodology, Experiment Conduction, Investiga­
tion, Data curation.
I-Sheng Ting: Experiment Conduction, Data curation, Manuscript
revision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This research was funded by the Ministry of Science and Technology
of Taiwan under the contact MOST 108-2221-E-007-059-MY2.
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