E L S E VI E R Surface and Coatings Technology 74 75 (1995) 135-142

Compari son of fundamental properties of r.f.-sputtered Ti Nx and Hf N x

coati ngs on steel substrates
G. Berg, C. Friedrich, E. Broszeit, K.H. Kl oos
Institute of Materials Science, Technical University of Darmstadt, Grafenstrafle 2, D-64283 Darmstadt, Germany
Abstract
Titanium and hafnium based coatings in this work were sputtered on steel substrates in a r.f. sputtering unit with a diode
arrangement. By feeding nitrogen in addition to the inert processing gas argon, TiN x and HfN x coatings were deposited under
reactive sputtering conditions. Deposition pressure, nitrogen flow in the chamber and bias voltage on the substrates were
systematically varied to get optimized coating systems.
The coatings were investigated on their fundamental properties in order to compare titanium and hafnium based films, sputtered
under identical process conditions.
The results for hardness, deposition rate, internal stress, adhesion, structure, phase analysis and wear show that the properties
of HfNx coatings are less influenced by the deposition process than the coatings of TiNx in the field of selected deposition
parameters. The behavior of HfN x is comparable to TiNx, owing to a very similar crystal structure of the materials, but the
conclusion of this present paper the well known TiNx has to be preferred for tribological applications in mechanical components.
Keywords: PVD coatings; Sputtering; Coating properties; Titanium nitride; Hafnium nitride
1. Introducti on
Ha r d coat i ngs deposi t ed by means of physi cal va por
deposi t i on ( PVD) are well est abl i shed in wear pr ot ect i on
in addi t i on t o ot her appl i cat i ons, e.g. har d coat ed cut t i ng
t ool s wi t h l ong lifetime [ 1] . I n this cont ext Ti N films
are well known for qui t e hi gh har dness and sui t abl e
adhesi on whi ch are i mpor t a nt in the field of t ri bol ogy.
Thi s l eads t o ext ended use of Ti N for t he wear pr ot ect i on
of machi ne c ompone nt s and tools.
For ma ny years Ti N has been a s t andar d coat i ng for
a wide r ange of subst r at e mat eri al s. Si mi l ar pr oper t i es
t o Ti N can be expect ed by usi ng coat i ngs based on
met al s si mi l ar t o t i t ani um, for exampl e haf ni um I - 2- 4] .
Ref. [ 5] r epor t s very hi gh har dness of Hf N coat i ngs of
over HV 6000. Besides this, Oakes r epor t s in Ref. [ 6]
l owest wear for Ht N coat ed cut t i ng t ool s. For this r eason
the basi c mechani cal and t r i bol ogi cal pr oper t i es of haf-
ni um based ni t ri des in compar i s on t o t i t ani um based
ni t ri des are the subject of t hese i nvest i gat i ons. The
coat i ngs in this pa pe r were pr oduced under i dent i cal
sput t er i ng condi t i ons in or der t o give al so an i mpr essi on
of the different deposi t i on behavi or of Ti Nx and Hf Nx
usi ng the same deposi t i on process.
Hf and Ti .... f ound in the same gr oup of the per i odi c
0257-8972/95/$09.50 1995 Elsevier Science S.A. All rights reserved
SSDI 0 2 5 7 - 8 9 7 2 ( 9 5 ) 0 8 2 9 9 - 9
t abl e of el ement s - - show, for exampl e, the same hexago-
nal cryst al st r uct ur e and f or mal oxi dat i on states, whereas
the densi t y as well as ot her pr oper t i es of the pur e met al ,
like the at omi c mass, differ.
In or der t o have a br oa d field for the i nvest i gat i ons
and the results, the deposi t i on par amet er s of ni t r ogen
flow, bi as vol t age and pr essur e were changed. These
mai nl y affect the f undament al pr oper t i es of sput t er ed
PVD coat i ng syst ems [ 7] . The pr oper t i es shown in the
paper were exami ned wi t h c ommonl y used met hods of
surface anal ysi s and t r i bol ogy [ 8] .
2. Experi ment al detai l s
2.1. Sputtering system and parameters.for coating
deposition
The coat i ngs were pr oduced by means of a commer ci al
r.f. sput t er i ng uni t (Alcatel SCM 601). The gl ow dis-
char ge was suppl i ed by a gener at or of 13.56 MHz wi t h
spl i t t abl e power in or der t o per f or m sput t er cl eani ng of
t he subst r at es as well as r.f. bi as sput t eri ng.
All coat i ngs were pr oduced wi t h the s ame geomet r i cal
condi t i ons in t he sput t er i ng unit, the same r.f. power
136 G. Berg et al./Surjace and Coatings Technology 74 75 (1995) 135 142
and an equal time of sputtering. Also the cleaning of the
substrates, made of ball beari ng steel (SAE 52100; DI N
1.3505) and casting steel ( DI N 1.0443), using ul t rasoni cs
and special cleaners based on al cohol as well as sput t er
cleaning in pur e ar gon at mospher e ( Us = - 6 0 0 V and
p = 1.5 Pa for 20 min) was unchanged.
A t hi n i nt ermedi at e l ayer of the pur e met al was
deposi t ed fol l owed by a thin gradi ent coat i ng of ni t rogen
up t o the desired film paramet ers.
The field of deposi t i on par amet er s is described by the
ni t rogen flow beginning with 0 cm 3 min 1 up t o 7.5 cm 3
mi n- 1 which allows several phases t o be examined. The
var i at i on of the bias vol t age has changed from floating
pot ent i al (approx. +2 0 V), gr ound pot ent i al t o a nega-
tive bias vol t age of - 40 V. The pressure of the worki ng
gas increased onl y from 1.0 Pa t o 2.0 Pa.
values shown l at er on were t aken under l oadi ng condi -
tions. In this case elastic and plastic def or mat i on are
measur ed t oget her. Ther ef or e the values for t he hardness
are not so high as the values represent i ng onl y the
plastic deformat i on.
2.2.4. X-ray diffractometry
X-ray diffraction was used t o st udy the phases and t o
measure i nt ernal stress on the surface. The equi pment
was a 0- 20- goni omet er (Siemens D 5000) with Eul er
cradl e for ~b-rotation, with grazi ng i nci dent -angl e 7,
secondar y monoc hr oma t or and scintillation count er for
peak det ect i on. The i nt ernal stress was measur ed by the
sinZ@ met hod and the peak posi t i ons were eval uat ed by
using the cent er of gravi t y met hod.
2.2. Characterization of coatings
It is necessary t o define some abbrevi at i ons for the
nitrides of t i t ani um and hafnium. Keepi ng in mi nd t hat
all coat i ngs pr oduced were mul t i phase coat i ngs (except
the coat i ngs based on the pur e metals) Ti N and Hf N
demonst r at e t hat the layers are domi nat ed by the stoi-
chi omet ri c phase. Ti N x and HfNx always means a field
of mul t i phase coatings based on t i t ani um and hafni um
nitrides with different met al t o ni t rogen rat i o (ot her
aut hor s use e.g. Ti - N or Ti (N)).
2.2.1. Deposition rates by the ball crater method
The thickness of har d coat i ngs influences di rect l y the
possible removal of the surface under t ri bol ogi cal l oad-
ing. To anal yze the thickness of t hi n films and to get the
deposi t i on rates rel at ed to special deposi t i on paramet ers,
the ball cr at er met hod [-8] allows pr ompt and sufficiently
precise results t o be obt ai ned. A cr at er is gr ound i nt o
the coat ed specimen by a steel ball of defined diameter,
wet t ed by a di amond suspension on an al cohol base.
The concent ri c circles are measur ed by mi cr oscopy and
the thickness is cal cul at ed f r om these data.
2.2.5. Scratch testing
For the eval uat i on of adhesi on, scrat ch testing was
selected. A commerci al CSEM Revetest scrat ch t est er
was used with a Rockwel l C i ndent er whi ch was dr awn
over the coat i ng surface with increasing force. Dur i ng
scrat chi ng on the one hand frictional force bet ween
di amond and t he coat i ng and on the ot her hand acoust i c
emission were cont i nuousl y moni t or ed. The results were
t hen verified by opt i cal mi croscopy.
2.2.6. Plate on cylinder wear test
Li near wear and friction coefficient were studied using
a plate on cyl i nder t ri bomet er. The coat ed plates made
of casting steel were tested against gr ound cylinders
made of SAE D2 ( DI N 1.2379). Nor mal force, testing
speed and sliding di st ance were varied, while dr y friction
at an ambi ent t emper at ur e of 23 + 3 C and relative
humi di t y of 50%_+6% were par t of the fixed test
condi t i ons. A di st ance sensor moni t or ed the l i near wear
and a force sensor i ndi cat ed the friction coefficient. The
results concer ni ng linear wear coul d be verified by
pr of i l omet r y plots of the tested coat i ng systems.
2.2.2. Morphology and thickness of the coatings by SEM
The mor phol ogy of the coat i ngs was anal yzed by
means of scanni ng el ect ron mi cr oscopy (Zeiss DSM
962). The specially pr epar ed specimens for these investi-
gations were br oken and the fract ure surfaces were
inspected. The thickness of the coat i ngs was also mea-
sured with SEM l ooki ng at right angles t o the fracture.
2.2.3. Dynamic ultra microhardness testing
The hardness was measur ed with a dynami c ul t ra
mi cr ohar dness t est er (Shi madzu DUH 202) using a
Vickers di amond, a force of 100 mN, a l oadi ng speed of
6.75 mN s 1 and a resting t i me of 10 s. The hardness
was anal yzed as a funct i on of force and depth. In
cont r ast t o the commonl y used Vickers hardness, the
3. Res ul t s
3.1. Influence of nitrogen flow on coating properties
3.1.1. Color
The first r emar kabl e influence of the ni t rogen flow on
the propert i es of the investigated har d coat i ngs is shown
by the col or of the films. Whereas Ti Nx coat i ngs st ay
gol den when the Ti N phase is built, the Hf N x coat i ngs
onl y show a gol den surface for a small range. At hi gher
flow rates for ni t rogen the films became dar k grey, in
cont r ast t o the pale grey in the range of l ower ni t rogen
values.
G. Berg et aL /Surface and Coatings Technology 74-75 (1995) 135-142 137
1 6 0
1 4 0
1 2 0
1 0 0
8 0
6 0
4 0
2 0
0
d e p o s i t i o n r a t e Deposition rate calculated from thickness
[ n m l m i n ] ~ ~ values measured by bal l crater testing
h e x a g o n a l ~ I I . " ~F~7" * r ~? II
, . i c e
HfN =.=
Ti TIN0.3 ~ "=---~-- - ~ "
- - - ~ I ~ " 3 9 . 9 - - . . . . . .
~ nm/ mi n cubi c l at t i ce ~
I
system: Alcatel SCM 601 ~ V Ti N =.. I 4 3 5
s u b s t r a ~ e t seperation: 65 mm ~ nm/ mi n
power: 750 W; pressure: 1.5 Pa
bias voltage: -20 V; time 160 min
i w w
0 1, 2 2 3 4 7 , 5
n i t r o g e n f l o w [ c m3 / mi n ]
Fi g. 1. I nf l ue nc e of n i t r o g e n f l ow on t he d e po s i t i o n r at e.
3.1.2. Deposition rate
The deposition rate is strongly influenced by the
sputtered metal first of all; the rates of Hf based coatings
are much higher then the rates of Ti based coatings.
Fig. 1 shows that the thickness values for Hf based
coatings are two to five times higher than for TiNx
layers of the studied parameter field. According to the
phases of the analyzed coatings, the deposition rate
decreases clearly when the stoichiometric TiN and HfN
phases with cubic lattice are detected. The hexagonal
lattice of the pure metals and the following substoichio-
metric nitrides at low nitrogen flow do not influence the
deposition rate in a characteristic way.
3.1.3. Structure and morphology
The phases analyzed by X-ray diffraction show the
hexagonal crystal lattices of the pure metals Ti and Hf.
The cubic phases TiN and HfN only exist at exactly
defined, rather high nitrogen flow rates. At these flow
rates of 3 cm 3 mi n- 1 for TiN and 4 cm a mi n- 1 for HfN
the best crystallinity is also found. The JCPDS standard
files sorted to the measured systems of coatings at low
nitrogen flow show further substoichiometric nitride
phases for both metal-nitrogen compounds correspond-
ing to TiNo,3 (ASTM card 41-1352) and HfNo, 4 (ASTM
card 40-1277). Tetragonal phases like Ti2N were not
detected by X-ray diffraction. The reason could be that
they occur only at a special deposition temperature,
which was not strictly controlled.
Increasing nitrogen flow leads to coatings showing an
extremely dense and fibrous structure as shown in Fig. 2
for the case of HfN x. The morphology of HfN x films
looks similar to that of TiN x, whereas the coating of the
pure hafnium appears more dense.
defined by the phases. In these investigations a compres-
sive stress state is always detected. Lowest stress was
detected for the pure metals Ti (approx. 0 N mm -2) and
Hf ( - 1000 N mm-2). Increasing nitrogen flow during
the deposition process - - restricted to a single phase - -
leads to higher internal stress values probably caused
by additional nitrogen located in the lattice. Generally
stoichiometric phases show lower compressive stress
values than nonstoichiometric phases.
3.1.5. Adhesion
Very important for any application of hard coatings
are the results on adhesion of the coatings. With respect
to the fact that the coatings were produced with the
same intermediate layers, the varying of the nitrogen
flow rate shows clearly that the coatings with stoichio-
metric phases are best. As pointed out in Fig. 3, nonstoi-
chiometric films studied in the range of the deposition
parameters could not reach this optimum.
3.1.6. Hardness
The hardness of PVD coatings, depending on the
deposition parameter nitrogen flow, seems to be mainly
influenced by the phases detected with XRD. Highest
hardness values (note that the hardness is measured
under loading conditions) were detected by analyzing
the stoichiometric phases TiN and HfN and also coatings
with lower nitrogen flow rates. It should also be kept in
mind that the internal stress conditions influence these
results. HfN ( DUH= l 1 5 7 Nmm -2) reaches a higher
hardness than TiN (DUH = 815 N mm-2}. The hardness
is, besides the deposition rate of the sputtering process,
the only fundamental property which is better for HfN
than for TiN.
3.1.4. Internal stress
The influence of the nitrogen flow rate on the internal
stress in the coatings of the first order is primarily
3.1.7. Friction and wear
To give a representative impression of the wear proper-
ties, Fig. 4 illustrates the results from the plate-on-
138 G. Berg et al./Surjdee and Coatings Technology 74 75 (1995) 135-142
cyl i nder test of l i near wear rat es and friction coefficients
for uncoat ed cast i ng steel (subst rat e mat er i al ) and the
pur e met al s Ti and Hf in r el at i on t o the st oi chi omet r i c
Ti N and Hf N phases. In cont r ast t o uncoat ed friction
par t ner s i ncreasi ng friction coefficients are t ypi cal l y
f ound for coat ed speci mens up t o a rat i o of nor mal force
to t angent i al force of 0.8. Bot h coat i ng syst ems give an
excellent wear reduct i on, but in the case of Ti N this is
appr oxi mat el y five t i mes mor e t han Hf N.
3.2. Inf l uence o f bias vol t age on coat i ng propert i es
3. 2. i. Col or
The col or of the Hf N coat i ngs did not change ma r k-
edly under the influence of the bi as vol t age. Onl y Ti N
is influenced in col or by appl yi ng no subst r at e bias
(reddish brown) and sput t er i ng under fl oat i ng bias condi -
t i ons (al most bl ack coat i ng). The col our of Ti N films
under moder at e bias vol t ages is dar k gol den wher eas in
compar i s on Hf N is pal e gol d for all bias condi t i ons.
3.2.2. Deposi t i on rat e
The deposi t i on rat es for Hf N x coat i ngs under the
gi ven sput t er i ng condi t i ons are much hi gher t han t hose
for Ti Nx. Compa r e d wi t h the rat es of Hf N pr oduced
under var yi ng bi as vol t age, the t hi ckness of the films
does not change very much. Devi at i ons f r om t he aver age
val ue are small ( < 10%). I n cont r ast t o this the depos-
i t i on rat e of Ti N coul d be influenced mor e st r ongl y in
t he studied r ange of bi as vol t age. The r at e decreases
cont i nuousl y wi t h i ncreasi ng negat i ve bi as to hal f the
val ue (still a rat e of 17 nm mi n t), when compar i ng
deposi t i on under a fl oat i ng pot ent i al with an appl i ed
bias vol t age of - 4 0 V.
3.2.4. Int ernal stress
The i nvest i gat i ons on i nt ernal stress det ect ed by X- r ay
di f f r act omet r y led t o the cl ear results shown in Fig. 5.
The bias vol t age har dl y influences Hf N, whereas the
i nt ernal stress of Ti N coat i ngs is mai nl y domi nat ed by
the bias vol t age.
l a)
Ib)
3.2.5. Adhesi on
The adhesi ve failure whi ch depends upon the bi as
vol t age on the subst r at es shows t hat moder at e val ues of
bi as lead t o the best results. Moder at e in this case means
a r ange of - 1 0 V t o - 3 0 V for bot h coat i ng syst ems
studied. Referri ng t o a wor ki ng gas pressure of 1.5 Pa
the ma xi mu m was f ound havi ng appl i ed - 2 0 V.
Haf ni um based coat i ngs also wi t h respect t o the adhesi on
coul d be less influenced t han t i t ani um nitride.
Fig. 2. Influence of nitrogen flow on structure and morphology of
HfN x coatings: (a) pure hafnium; (b) HfN (N2-4 cm 3 min- i); (c) HfN X
(N/= 7.5 cm 3 min 1).
(c}
G. Berg et al./Surface and Coatings Technology 74-75 (1995) 135-142 139
Results from 4 t~sts by optical analysis
Critical load = first point of adhesive failure
(failure at the eoating-to-substrate interface)
4
7,5
ni t r ogen f l ow [ cm3/ mi n]
Fig. 3. Infl uence of ni t r ogen flow on t he adhesi on.
90
80
70
60
50
40
30
20
10
0
l i near we a r [l~m]
la=0475
ii~i~
cast i ng
st eel
~ii~i~:~ testing conditions
plate-on-cylinder tri bometer
load: l kg; speed: 004 m/s;
distance: 300 m
H=0775 i ~ dry friction at room temperature
" N
~i ~i ~ ~:~ stoichiometric coatings
~%~i ~% bias voltage: -20 V; pressure: 1 5 Pa
~;~ilii ~i, ~t=0 70
~1
Ti Hf Ti N HfN
c o a t i n g s y s t e m
Fig. 4. Fri ct i on a nd wear pr oper t i es of t i t a ni um a nd ha f ni um and t hei r st oi chi omet r i c ni t ri de phases.
- 8000
I J
I / st ress evaluation by sin=~-method from
1 ~ " / ~ ' * (210) peak (Siemens diffractmeter D5000)
Young~s modulh E(TiN)=400000N/mm2; E(HfN)=380000N/mmZ; v=0.2
- 7000
E
-6ooo
z
- 5000
- 4000
E -3000
.E - 2000
- 1000
1000
f l o a t i n g g r o u n d -10 -20 -30 -40
bi as vol t age [V]
Fig. 5. Infl uence of bi as vol t age on t he i nt er nal st ress of Ti N a nd Hf N.
140 G. Berg et aL/Surface and Coatings Technology 74 75 (1995) 135-142
1600
1400
1200
1000
800
6 0 0
400
200
0
f l o a t i n g
u n i v e r s a l
h a r d n e s s / I TiN
[ N I m ~ ~ deviationsrepresent standard
dynamic universal hardness (Shimadzu DUH 202)
vickers indenter - load 100mN - speed 6,75mN/sec - after time 10sec
hardness under loading conditions
i = ! =
gr ound -10 -20 -30
Fig. 6. Infl uence of bi as vol t age on t he har dness.
-40
bi as vol t age [V]
3.2.6. Hardness
The influence of the appl i ed bias vol t age on the
hardness values of coatings for Ti N films is well known
and can be used t o pr oduce defined propert i es. Fig. 6
illustrates the hardness results by compar i ng mean values
of Ti N and Hf N under increasing bias voltage. The first
poi nt t o be ment i oned is the hi gher val ue for each Hf
based l ayer and the cor r espondi ng fact t hat a specific
influence is not possible. The hardness values measur ed
under floating pot ent i al condi t i ons are of the same size
as the one coat ed at - 4 0 V bias voltage. Ti N coul d
mor e easily be influenced and shows cont i nuousl y
increasing values for hardness with increasing negative
bias voltage. The results for hardness and i nt ernal stress
depend on each other.
3.3. Influence of deposition pressure on the coating
properties
3.3.1. Deposition rate
The deposi t i on rat e was st udi ed as a funct i on of the
pressure of the worki ng gas. The ar gon flow was changed
keepi ng the ni t rogen flow const ant . Because of the
change in part i al pressure of the gases the deposi t i on
rat e increases for bot h coat i ng systems with increasing
pressure. For Ti N the deposi t i on rat e of 10 nm mi n -1
at 1 Pa doubl es for coat i ngs pr oduced at 2 Pa.
3.3.2. Internal stress
Int ernal stress in Hf N was little influenced by the
vari at i on of pressure compar ed with Ti N. Fig. 7 displays
results from the XRD and the bendi ng beam met hod
concerni ng the influence of pressure on the i nt ernal
stress of Ti N films. The results f r om the qui t e simple
bendi ng beam met hod, which takes the def or mat i on of
a thin spring steel subst rat e under the effecting i nt ernal
stresses of the coatings, cor r espond clearly with the XRD
results, but always give l ower values t han the XRD
measurement .
3.3.3. Hardness
Har dness decreases for increasing ar gon pressure in
the range 1.0 2.0 Pa for Ti N f r om DUH = 1200 N mm -2
to 930 N mm- 2 and for Hf N f r om 1390 N mm = down
to 1155 N mm -2. The effect on Ti N is, like all changes
in deposi t i on paramet ers, st ronger t han t hat on HfN.
3.3.4. Further effects
The st ruct ure of the coat i ngs was not affected mar k-
edly by the change of pressure of the worki ng gas. The
relative small var i at i on in ar gon pressure also di d not
cause changes in color.
4. Discussion and conclusions
Invest i gat i ons i nt o deposi t i on of har d coat i ngs based
on the t i t ani um and hafni um nitrides were made t o
st udy whet her the propert i es of HfNx can equal or
possibly surpass qualities of Ti N. The research wor k
was done f r om the view of a pr oducer of coat i ngs for
special demands by varyi ng the basic par amet er s of the
reactive sput t eri ng process and the t arget material.
The f undament al propert i es of r.f. sput t ered Ti Nx and
Hf N x coat i ngs are in many cases similar but not the
same. Invest i gat i ons on coat i ngs sput t ered reactively
under the same process condi t i ons were made and gave
an overvi ew of the range of propert i es which can be
affected. For absol ut e values given in Figs. 1 7, Fig. 8
shows with a relative scale the range of results for the
studied coatings.
Concer ni ng the deposi t i on rat e of the investigated
t i t ani um and hafni um based nitrides, the rat e for HI N x
is always much hi gher using the same sput t eri ng par ame-
G. Berg et al./Surface and Coatings Technology 74-75 (1995) 135 142 141
- 6 0 0 0 -
E
E
p_ - 5 0 0 0
-4000
E - 3000
-2000
-1000
XRD stress evaluation by sin=~-method from (220) peak;
Siemens diffractometer D5000
Bending beam method using spring steel, d=0,1mm
E(HfN)=3S00OON/mmZ; v=0.2 2870
1 1,5 2
pressure [Pa]
Fig. 7. Infl uence of pr essur e on t he i nt er nal st r ess of Ti N.
._E
X
~ . >
E ~
E
100%
:::~ relative m
90% i~i E maximum ~k~ r~ itiv m~ ~
70*/, ~
so% ~ ~. '
30% '~ ~ f _ N l - = - i ~ N i ~
deposition r a t e compressive adhesion hardness
internal stress
Fig. 8. Range of resul t s, ma xi ma
test procedure
a nd mi ni ma of f unda me nt a l propert i es.
ters. Increasi ng ni t r ogen flow, domi nat ed by the phases
pr oduced, leads t o a significant decrease in t he deposi t i on
rate. A var i at i on of the bias vol t age on the subst rat es at
the best st oi chi omet ri c phases show a st rong influence
on the Ti N coat i ngs while Hf N was onl y slightly affected.
For the appl i cat i on of these coat i ngs on t ool s or
machi ne part s t here are t wo i nt erest i ng facts. Hf N coat -
ings for t ri bol ogi cal use with mi ni mal coat i ng thickness
coul d be pr oduced in a shor t er t i me and the process is
not ver y sensible accor di ng t o the process par amet er s
e.g. bias vol t age, so the pr oper t i es are easier t o r epr oduce
for Hf N t han for Ti N.
Also t he hardness is hi gher for the Ht N x coat i ngs
st udi ed compar ed with i dent i cal l y pr oduced Ti Nx.
Hi ghest hardness values were f ound for slightly overs-
t oi chi omet r i c films. Again Ti Nx was much mor e influ-
enced t han Ht Nx. Thi s result also poi nt s out t hat
sput t eri ng Hf N x is easier because the hardness is al most
i ndependent of the deposi t i on paramet ers.
The i nvest i gat i ons on i nt ernal stress lead t o similar
results. Thi s is caused by the di rect cor r el at i on of i nt ernal
stress and hardness. The hafni um based nitrides were
nearl y not affected whereas for t i t ani um ni t ri de compres-
sive i nt ernal stress increases a lot wi t h bias voltage. In
or der t o pr oduce coat i ngs with defi ned high or low
i nt ernal stress, we concl ude t hat onl y t i t ani um ni t ri de
coul d do this in t he field of par amet er s studied.
Accordi ng t o t he adhesi on of the coat i ngs with an
i nt ermedi at e l ayer of the pur e met al s t i t ani um or haf-
nium, st oi chi omet ri c Ti N and Hf N coat i ngs show highest
values. Also moder at e bias voltages ( ~ - 2 0 V) on the
subst rat e lead t o the best results. Thi s behavi or is of
great i nt erest because the i nt er medi at e layers for all
coat i ngs of one met al were identical. So adhesive failure
is not domi nat ed by the i nt ermedi at e coating.
Compar i ng the identically sput t ered coat i ngs on tita-
ni um and hafni um bases, the Ti Nx films are bet t er in all
cases. That is very i mpor t ant for the appl i cat i on of these
films on machi ne part s or t ool s because the best physical
pr oper t i es of a coat i ng system coul d not be used if the
adhesi on is not sufficient for the t ri bol ogi cal demands.
Fi rst i nvest i gat i ons on the t ri bol ogi cal behavi or of the
142 G. Berg et al./SurJace and Coatings Technology 74-75 (1995) 135-142
studied coat i ngs in a pl at e-on-cyl i nder t r i bomet er show
t hat the linear wear is much bet t er for Ti N t han for
Hf N al t hough Ti N was found t o have a hi gher friction
coefficient.
Looki ng at the par amet er s for coat i ng deposi t i on the
ni t rogen flow allows a wide rangi ng influence on the
coat i ng propert i es. Dependent on the phases pr oduced,
deposi t i on rate, mor phol ogy and adhesi on can be vari ed
over a wide range. The influence of bias vol t age on the
subst rat es is most i mpor t ant on the i nt ernal stress of the
coat i ngs and the hardness. Eval uat i ng t he influence of
the i nert gas pressure, the change in part i al pressure
must be seen in addi t i on t o the influence of pressure of
the worki ng gas itself.
The charact eri st i c propert i es of the Hf N x coat i ngs
coul d be much less influenced by the par amet er s appl i ed
duri ng the sput t eri ng process t han the TiNx layers. Thi s
must be expl ai ned by the high at omi c mass of the
el ement hafni um compar ed t o t hat of titanium.
Thi s is i mpor t ant for the appl i cat i on of the coat i ngs
because slight differences in sput t eri ng does not lead t o
mar ked differences in physical and mechani cal pr oper -
ties. Also the high deposi t i on rat e for hafni um ni t ri de
coat i ngs is an advant age in rel at i on t o the coat i ngs
based on titanium. To opt i mi ze Hf N x coat i ngs furt her
investigations shoul d be done by furt her opt i mi zat i on
of the deposi t i on paramet ers.
At least we must state t hat in these i nvest i gat i ons Ti N
coat i ngs showed bet t er basic mechani cal propert i es,
especially for the very i mpor t ant adhesi on of the films.
Ther ef or e Hf N coul d not subst i t ut e t he funct i on of Ti N
due t o wear prot ect i on. For these reasons t i t ani um
nitride seems t o be still the bet t er choi ce of har d coat i ng
for tribological applications.
Acknowledgements
Thi s wor k is par t of the Schwer punkt pr ogr amm l onen-
und Plasmaoberfl~ichentechnik of the Deut sche
Forschungsgemei nschaft . The aut hor s wish t o acknow-
ledge financial support .
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