Department of Physics, Chemistry and Biology

Master Thesis
Growth and Phase Stability of
Titanium Aluminum Nitride Deposited by
High Power Impulse Magnetron Sputtering
Chung Chuan !ai
LiTH-IFM-A-!--""#$%&%--'
'(per)isor* +ostas 'ara,inos, Lin,-pings (ni)ersitet
!aminer* .lf Helmersson, Lin,-pings (ni)ersitet
Department of Physics, Chemistry and Biology
Lin,-pings (ni)ersitet
'-%/" /& Lin,-ping, '0eden
Titel
Title*
1ro0th and Phase 'ta2ility of Titani(m Al(min(m 3itride Deposited 2y High Po0er
Imp(lse Magnetron 'p(ttering
"#rfattare
A(thor*
Ch(ng Ch(an, Lai
Sammanfattning
A2stract*
In this 0or,, 0e in)estigate the relation 2et0een the diff(sion 2eha)ior of Ti1-xAlx3 at ele)ated temperat(res and the microstr(ct(re4 Thin
film samples are synthesi5ed 2y reacti)e co-sp(ttering 0ith t0o cathodes4 6ne cathode e7(ipped 0ith Ti target is connected to a high
po0er imp(lse magnetron sp(ttering 8HiPIM'9 po0er s(pply, and the other cathode e7(ipped 0ith Al target is operated 0ith a direct
c(rrent po0er so(rce4 The spinodal decomposition of c(2ic metasta2le Ti1-xAlx3 controlled 2y thermally acti)ated diff(sion is o2ser)e for
diff(sion 2eha)ior4 :ario(s HiPIM' p(lsing fre7(encies are (sed to achie)e different microstr(ct(re, 0hile altered po0er applied to Al
target is (sed to change the Al content in films4 In the phase composition analysis achie)ed 2y 1I-;<D, the right-shift of 8"""9 film pea,
along 0ith increasing Al-po0er is o2ser)ed4 A sat(ration of the right-shift and h-Al3 pea,s are also o2ser)ed at certain Al-po0er4 The
chemical composition determined 2y <DA sho0s trends of red(cing Al sol(2ility limit in metasta2le phase and 6 contamination (pon
decreasing the p(lsing fre7(ency4 More 3 deficiency is fo(nd in samples deposited 0ith higher fre7(ency4 In the %== H5 and $%= H5
samples deposited into similar composition and thic,ness, no apparent difference of the microstr(ct(re is o2ser)ed from the 'M cross-
sectional images4 From HT-;<D, 0e o2ser)e higher intensity of Ti6$ and h-Al3 pea,s in %== H5 sample at ele)ated temperat(re as
compared 0ith $%= H5 one4 From the red(ction of 6 contamination, denser Ti1-xAlx3 films are a2le to 2e deposited 0ith lo0er HiPIM'
p(lsing fre7(ency4 In addition, the higher intensity o2ser)ed in HT-;<D patterns indicates that the %== H5 sample is more open to
diff(sion and therefore allo0s the ne0 formed phases to gro0 in larger grains4
Ny$%elord
+ey0ord*
HiPIM', co-sp(ttering, diff(sion, microstr(ct(re, spinodal decomposition, Ti
1-x
Al
x
3
A&delning Institution
Plasma and Coatings Physics
Department of Physics, Chemistry and Biology
Lin,-ping .ni)ersity
Datum
Date
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IS2N
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Serietitel o$h serienummer ISSN
Title of series, n(m2ering
Handledare
'(per)isor* +ostas 'ara,inos
3rt
Location* Lin,-ping
2apporttyp
<eport category
Licentiata)handling
! !amensar2ete
C-(ppsats
D-(ppsats
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Spr4%
Lang(age
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ABSTRACT
In this 0or,, 0e in)estigate the relation 2et0een the diff(sion 2eha)ior of Ti
1-x
Al
x
3 at
ele)ated temperat(res and the microstr(ct(re4 Thin film samples are synthesi5ed 2y reacti)e
co-sp(ttering 0ith t0o cathodes4 6ne cathode e7(ipped 0ith Ti target is connected to a high
po0er imp(lse magnetron sp(ttering 8HiPIM'9 po0er s(pply, and the other cathode e7(ipped
0ith Al target is operated 0ith a direct c(rrent po0er so(rce4 The spinodal decomposition of
c(2ic metasta2le Ti
1-x
Al
x
3 controlled 2y thermally acti)ated diff(sion is o2ser)e for diff(sion
2eha)ior4 :ario(s HiPIM' p(lsing fre7(encies are (sed to achie)e different microstr(ct(re,
0hile altered po0er applied to Al target is (sed to change the Al content in films4 In the phase
composition analysis achie)ed 2y 1I-;<D, the right-shift of 8"""9 film pea, along 0ith
increasing Al-po0er is o2ser)ed4 A sat(ration of the right-shift and h-Al3 pea,s are also
o2ser)ed at certain Al-po0er4 The chemical composition determined 2y <DA sho0s trends
of red(cing Al sol(2ility limit in metasta2le phase and 6 contamination (pon decreasing the
p(lsing fre7(ency4 More 3 deficiency is fo(nd in samples deposited 0ith higher fre7(ency4 In
the %== H5 and $%= H5 samples deposited into similar composition and thic,ness, no apparent
difference of the microstr(ct(re is o2ser)ed from the 'M cross-sectional images4 From HT-
;<D, 0e o2ser)e higher intensity of Ti6
$
and h-Al3 pea,s in %== H5 sample at ele)ated
temperat(re as compared 0ith $%= H5 one4 From the red(ction of 6 contamination, denser
Ti
1-x
Al
x
3 films are a2le to 2e deposited 0ith lo0er HiPIM' p(lsing fre7(ency4 In addition, the
higher intensity o2ser)ed in HT-;<D patterns indicates that the %== H5 sample is more open
to diff(sion and therefore allo0s the ne0 formed phases to gro0 in larger grains4
i
ii
ACKNOWLEDGEMENT
Before starting this article, I 0o(ld li,e to sho0 all my appreciation to the people 0ho
s(pported me finishing this 0or,, in e)ery aspect4 Ditho(t any of yo(, the 0or, 0ill ne)er 2e
done4 I 0o(ld li,e to than,
5lf Helmersson, for accepting me as a mem2er in the Plasma and Coating Physics gro(p4
Eo(r patient listening and ,no0ledge al0ays ma,e the disc(ssion 0ith yo( helpf(l4 I am )ery
happy for the time in yo(r gro(p, than, yo( and yo(r politenessF
6ostas Sara%inos, for 2eing an e!cellent s(per)isor 0ho al0ays gi)es me time from yo(r
intensi)e sched(le for disc(ssing and gi)ing ad)ices4 I am )ery gratef(l for yo(r patient
g(idance helping me 0or, thro(gh all the tro(2les4 Eo(r enco(ragement for trials and the
f(nny tal, 0ith yo( at leis(re time gi)es me a nice e!perience to 0or, 0ith yo(, than, yo(F
Asim Ai7a8, for 2eing a great teacher and friend 0ho al0ays enco(rages and help me 0hen I
st(c, 0ith pro2lems4 Eo( ta(ght me all the la2 operation at d0ard in the 2eginning of my
0or, in detail and arranged yo(r 0or,-time G(st for my e!periments, than, yo(F
Daniel Magnf9lt, for yo(r introd(ction at 1inn(ngagap and sharing yo(r e!perience on the
0or,4 specially yo( sa)ed my samples in the cham2er for se)eral times4 It is happy and
meaningf(l to disc(ss 0ith yo( a2o(t the 0or,, than, yo( and yo(r 2oo,sF
:ens :enson, for the <DA meas(rement4 Eo(r e)al(ations for the data and e!planations for
the plots are )ery helpf(l, than, yo(F
:ens 'ir$h and "redri% )ri%sson, for all the ;<D lect(res and t(torials that yo( 2ring4 Eo(
iii
are al0ays 0illing to help me sol)ing the pro2lem of the patterns and gi)ing priceless
e!periences, than, yo(F
!eif :ohansson, for yo(r instr(ctions of the department4 Eo(r help is )ery important, 0hich
ma,es me 0or,ing smoothly here, than, yo(F
Agne ;u%aus%aite, for yo(r help of sample polishing and yo(r nice instr(ctions4 Tal,ing
0ith yo( d(ring depositions is al0ays happy, than, yo(F
Petter !arsson, for sol)ing all ,inds of technical pro2lems d(ring the e!periment4 Eo(r
ad)ices a2o(t the s(2strate for high temperat(re e!periment really helped my 0or,
proceeding to the final stage4 Than, yo( and the Ta s(2strate yo( 2ro(ght to meF
Mattias Samuelsson, for the scientific articles that yo( ga)e me, no matter they are related to
my 0or, or G(st my interest4 I 2enefited a lot from yo(r g(idance of 'M and the disc(ss 0ith
yo( a2o(t 'M images4 Than, yo( and yo(r licorice candyF
Daniel !undin, for the nice disc(ssion a2o(t plasma physics4 Eo( e!plained me yo(r doctoral
thesis patiently and ga)e me helpf(l tips a2o(t opposing, than, yo(F
Montri Aiempana%it, for yo(r e!perience a2o(t reacti)e sp(ttering in detail4 It is also )ery
happy to ha)e a chat 0ith yo( 0hen yo( ha)e time4 Than, yo( and yo(r so()enirF
Group members, for offering me a nice 0or,ing space and atmosphere in the Plasma and
Coating Physi$s gro(p4
'o !<, for 2eing my 2est friend in '0eden and fighting together for o(r master degree4 I
appreciate a lot to all yo(r genero(s s(pport and treatment as a host4 Eo( and yo(r family
offered me a nice and (nforgetta2le feast d(ring the Chinese 3e0 Eear4 Than, yo( and yo(r
lo)ely family mem2ers4
Magnus 6arlsson, =i%tor :ohansson, and Peter :ason, for gi)ing me a nice office space
and rela!ing tal,s4 All yo( s(pport is necessary4 specially for :i,tor, 0ho spent many ho(rs
re2(ilding the deposition system 0ith me for tho(sand times4 Than, yo( allF
My whole family, for al0ays 2eing my 2est and last 2ac,(p thro(gh all time4 'orry for
ma,ing yo( 0orry and than, yo( for yo(r (nderstanding d(ring this st(dy4 Ditho(t yo( and
0hat yo( pro)ide for me, I 0ill ne)er stand in this height4 Than, yo( allF
i)
TABLE OF CONTENTS
1 INTRODUCTION............................................................................................1
1.1 Background and Motivation......................................................................1
1. Ai! and R"#"arc$ Strat"g%......................................................................&
2 Ti-Al-N TERNARY SYSTEM..........................................................................7
.1 Ti'A('N.......................................................................................................)
. S*inoda( D"co!*o#ition.........................................................................11
3 FUNDAMENTALS OF THIN FILM DEPOSITION........................................13
+.1 T$" S*utt"ring ,roc"##..........................................................................1+
3.1.1 The Magnetron Sputtering Process................................................14
3.1.2 The Reactive Sputtering Process...................................................15
3.1.3 High Power Impulse Magnetron Sputtering....................................1
+. T$in Fi(! Nuc("ation and Gro-t$...........................................................1)
4 THIN FILM ANALYSIS METHODS..............................................................21
&.1 .'Ra% Di//racto!"tr%..............................................................................1
4.1.1 The S!mmetrical "#2" $on%iguration...............................................23
4.1.2 The &ra'ing Inci(ence $on%iguration.............................................23
&. Scanning E("ctron Micro#co*%...............................................................+
&.+ E(a#tic R"coi( D"t"ction Ana(%#i#...........................................................0
)
5 EXPERIMENT..............................................................................................29
6 RESULTS AND DISCUSSION.....................................................................35
7 SUMMARY AND FUTURE OUTLOO........................................................45
! REFERENCES.............................................................................................47
)i
1 1NTROD2CT1ON
1.1 "#$%&'()*+ #*+ M(,i-#,i(*
Thin films and coatings
"
are microstr(ct(res 0ith thic,nesses ranging from a fe0 nanometers
(p to se)eral micrometers and they are (sed to modify the s(rface properties of a gi)en
material 8s(2strate94 Already from the ancient time of history, metal or alloy films 0ith
preferred colors or metallic reflections 0ere applied on s(2strates for decorati)e p(rposes H"I4
The film material that time had to possess a good mallea2ility, in order to red(ce its thic,ness
scale and to apply the coating (niformly onto the s(rface of the (nderlying s(2strate4
3o0adays films are synthesi5ed 0ith different compositions and str(ct(res to e!pand and to
enhance their f(nctionality and they are (sed in )ast range of technologically rele)ant areas,
s(ch as, optics, microelectronics, 2io-medicine, data storage, s(rface protection of c(tting
tools and machine component4 Titani(m al(min(m nitride 8Ti-Al-39, 0hich is the topic of the
present thesis, is a typical e!ample of film material for s(rface protection of c(tting tools
operating at ele)ated temperat(res H$I4
A large n(m2er of films are employed to protect 2(l, materials from en)ironmental physical
or chemical damages4 These films may 0ell e!hi2it higher hardness, higher to(ghness,
smaller friction coefficient, 2etter 0ear resistance, and 2etter chemical sta2ility as compared
to the (nderlying s(2strate materials4 Ceramics s(ch as metal nitrides, o!ides, car2ides and
silicides 0ere the materials to 2e (sed already from the early-mid "C==Js for the p(rpose of
" Tho(gh the terms thin film, film and coating are different in some aspects, they 0ill 2e hereinafter
(sed interchangea2ly thro(gho(t the thesis4
"
protecti)e coatings H&I4 The early stage of research on ceramics foc(sed on the 2inary
compo(nds 8e4g4 DC and TiC9, d(e to lesser comple!ity and easier control of 2inary systems4
Ti3 is among the 2est-,no0n and -st(died 2inary systems4 It 0as the first commerciali5ed
hard coating for c(tting tools in the history, 2eca(se of its o(tstanding 0ear resistance and
moderate hardness4 It is also )ersatile d(e to its e!cellent electrical cond(cti)ity, rather small
diff(si)ity to many aggressi)e chemicals and gases, and )ery fa)ora2le gold-colored
appearance4 It has ser)ed as an e!cellent hard coating material for more than K= years, 0hile it
is still fre7(ently (sed in fields other than s(rface protection HKI4
Altho(gh Ti3 is a 0ell-esta2lished hard protecti)e coating sol(tion, its o!idation resistance at
ele)ated temperat(res sets a critical limitation to the operation conditions4 specially d(ring
the operation of c(tting tools coated 0ith Ti3, the temperat(re increase ind(ced 2y the
friction 2et0een the tool and its co(nter s(rface at the contact is ine)ita2le for most cases4 Ti3
has a thermodynamically fa)ored tendency to replace the 2onded nitrogen 0ith gas o!ygen
molec(le, follo0ing 2y the o(t-gassing of nitrogen4 This o!idation process is acti)ated
thermally 2et0een %== LC to M== LC, lea)ing o!idi5ed titani(m 0ith red(ced hardness on the
s(2strate4 Along 0ith its 2ad 0ear resistance and adhesion, the titani(m o!ide layer is either
remo)ed or delaminated soon, e!posing fresh Ti3 coating 8to 2e o!idi5ed repeatedly9 or
s(2strate leading to tool fail(re H%, >, M, /I4 In order to impro)e the o!idation 2eha)ior of Ti3,
in the mid "C/=Js Al has 2een added forming the Ti-Al-3 ternary system HC, "=, "", "$I4 The
Al has higher mo2ility than Ti mo)ing thro(gh the parent phase and the o!ides of titani(m
and al(min(m, 0hich ma,es Al to 2e o!idi5ed more in amo(nt than Ti4 The o!idi5ed Al forms
a dense al(min(m o!ide layer on the s(rface of the coating, 0here the layer can effecti)ely
retard f(rther penetration of o!ygen and e!tend the life-time as compared to p(re Ti3 H>, M,
"&I4
Additional ad)antages 2esides the enhanced o!idation resistance 2y adding Al into Ti3 0ere
also reported in the late "C/=Js4 6ne 0as the impro)ement of mechanical properties of the
coatings 0ith respect to the 2inary co(nterparts Ti3 and Al34 Many gro(ps o2ser)ed increase
of the hardness of Ti-Al-3 coatings d(ring heat treatment a2o)e M== LC H>, M, "K, "%, ">, "MI
and aro(nd "CC=s, mechanisms 0ere proposed to e!plain this 2eha)ior4 The mechanisms 0ere
2ased on the age hardening effect triggered 2y a thermodynamic phenomenon, ,no0n as the
spinodal decomposition4 'pinodal decomposition creates domains 0ith different composition
in the coatings retarding the motion of dislocations H"/, "C, $=, $"I4 6hn(ma et al4 H$$I f(rther
$
s(ggested that d(ring spinodal decomposition Ti- and Al-rich domains 8c-Ti3 and c-Al3 rich
domains9 are formed from the metasta2le Ti
1-x
Al
x
3 matri!4 The spinodally decomposed
domains e!hi2it more fa)ora2le 2eha)iors in tri2ology tests, as opposed to the
thermodynamically sta2le phases, 8i4e4 c-Ti3 phase 0ith 0(rt5ite Al394 Mayrhofer et al4 H$&I
presented e)idence for the spinodal decomposition of Ti
1-x
Al
x
3 coatings 2y thermal analy5ing
the heat flo0 d(ring the decomposition, along 0ith o2ser)ations in the changes of phase
compositions and microstr(ct(res4
It is therefore e)ident from the pre)io(s paragraphs that (nderstanding of the atomistic
mechanisms that determine the phase sta2ility of metasta2le Ti
1-x
Al
x
3 is a prere7(isite for
de)eloping e!perimental strategies that 0o(ld allo0 for synthesis of Ti
1-x
Al
x
3 films 0ith
s(perior properties H$$I4 The Al3 content 0ithin the metasta2le phase is directly related to the
phase sta2ility of the system, 0here the higher Al3 content leads to a greater dri)ing force for
decomposition of Ti
1-x
Al
x
3 coatings in terms of thermodynamics4 Tho(gh 2etter performance
0ith respect to o!idation resistance and mechanical properties of films can 2e o2ser)ed 0ith
increasing the Al3 content, the degradation of a2o)e properties 0ill ta,e place 0hen the
sol(2ility limit of Al3 is e!ceeded4 In order to o2tain 2etter control of its phase sta2ility and
decomposition 2eha)ior related 0ith Al3 content, the sol(2ility limit of the Ti
1-x
Al
x
3 solid
sol(tion 0as in)estigated4 The e!perimental and comp(tational sol(2ility limit of the
Ti3-Al3 system ha)e 2een reported 2y many gro(ps H$$, $&, $K, $%, $>, $MI, 0here it
typically ranges from %= to M= N Al3 0ithin the solid sol(tion for different gro0th
conditions4
The gro0th conditions for sp(ttering 2ased physical )apor deposition 8P:D9 processes and
their res(lting microstr(ct(re and mechanical properties of the Ti
1-x
Al
x
3 coatings ha)e 2een
e!amined as 0ell4 D(hrer et al4 H$/, $CI reported that 2y increasing the po0er applied to the
cathode, higher micro-hardness of Ti
1-x
Al
x
3 films can 2e achie)ed as a res(lt of the grain
refinement4 'hetty et al4 H&=I reported that less poro(s and harder Ti
1-x
Al
x
3 films can 2e gro0n
2y depositing films at relati)ely high s(2strate 2ias )oltages and temperat(res4 6n the other
hand, the energetic 2om2ardment d(ring gro0th can increase the mo2ility of adatoms,
changing the microstr(ct(re and acti)ating decomposition of the metasta2le phase e)en 0ithin
the sol(2ility limit H&"I4 In)estigating the res(lting microstr(ct(re of the films is a good
approach to trace 2ac, the gro0th ,inetics4 Adi2i et al4 H&$I o2ser)ed the incoherency 0ithin
the microstr(ct(res d(e to the phase separation 0ith electron diffraction patterns and the
&
phase transformation 0ith !-ray diffraction 0hen increasing the s(2strate temperat(re d(ring
deposition4 They concl(ded that high Al3-content can only 2e achie)ed 2y thin film gro0ing
(nder ,inetically-limited conditions, e4g4, moderate s(2strate heating and ion 2om2ardment4
It is also ,no0n that the spinodal decomposition is a thermodynamically spontaneo(s process,
and this decomposition is initiali5ed 2y thermally acti)ated diff(sion for atoms in the parent
phase4 'ince diff(sion processes are ,no0n to 2e affected 2y microstr(ct(re H&&I, 0e see, to
e!plore the feasi2ility of controlling decomposition ,inetics and phase sta2ility of TiAl3 at
ele)ated temperat(res thro(gh control of microstr(ct(re of the films4 In order to in)estigate
this, a gro0th process 0ith capa2ility of microstr(ct(re modification is needed4
High power impulse magnetron sputtering (HiPIMS), is a thin film deposition techni7(e that
e!hi2its enhanced capa2ility of controlling the film microstr(ct(re as compared to
sp(ttering-2ased state of the art approaches4 The HiPIM' process allo0s for the generation of
an (ltra dense plasma 0hich leads to ioni5ation degrees of the sp(ttered material m(ch larger
than those achie)ed in con)entional magnetron sp(ttering techni7(es, e4g4 direct c(rrent
magnetron sp(ttering 8DCM'94 The plasma conditions of HiPIM' process greatly enhance the
fl(! of energetic ioni5ed species to0ards the gro0ing film d(ring deposition H&KI4 The
energetic fl(! a)aila2le at the s(2strate is a rather important feat(re in sp(ttering-2ased
deposition methods, since they transfer moment(m to the deposited layers tailoring the
adatom mo2ility4 This in t(rn pro)ide means for affecting the film microstr(ct(re, as 0ell as
the res(lting properties4 Many 0or,s ha)e sho0n the effect of the enhanced energetic fl(!es
d(ring HiPIM', 0hich incl(des gro0th of smooth and dense films H&%, &>I, impro)ement of
film adhesion and deposition of more (niform films on comple!-shaped s(2strates H&>, &MI4 In
addition, it has 2een reported that 2y t(ning process conditions in the HiPIM' parameter
space, e4g4 the fre7(ency, the p(lse 0idth and the target c(rrent, different microstr(ct(res can
2e achie)ed H&KI4 These changes of the microstr(ct(re 0ithin the film may affect diff(sion
process d(ring thermal treatment at ele)ated temperat(res4
1.2 Ai. #*+ R/0/#'$1 S,'#,/&2
The goal of this 0or, is to in)estigate and (nderstand the relation 2et0een the microstr(ct(re
and the phase sta2ility of Ti
1-x
Al
x
3 films at ele)ated temperat(res4 HiPIM' deposition process
is (sed d(e to its capa2ility of controlling the ioni5ation of sp(ttered material 2y changing the
HiPIM' operation parameters, e4g4 the a)erage po0er density and the p(lse shape4 The degree
K
of ioni5ation determines the ion 2om2arding 2eha)ior at s(2strate, affecting the deposition
,inetics and the res(lting microstr(ct(re of the gro0ing film4 A )ariety of fre7(encies 0ith the
same p(lse 0idth are employed4 All samples are prepared 2y reacti)e co-sp(ttering 0ith t0o
cathodes (nder constant flo0 of sp(ttering gas Ar and reacti)e gas 3
$
4 6ne cathode e7(ipped
0ith Ti target is connected to a HiPIM' po0er s(pply, 0hile the other cathode e7(ipped 0ith
Al target is fed 2y a DCM' po0er s(pply4 'eries of samples 0ith different Al-content are first
deposited to o2tain desired Al-content 0hile maintaining the c(2ic metasta2le phase for
TiAl3 prior to the thermal analysis4 The film chemical compositions is determined 2y elastic
recoil detection analysis 8<DA9 and the phases composition are in)estigated 2y gra5ing
incident !-ray diffractometry 81I-;<D94 'amples gro0n 2y different HiPIM' p(lsing
fre7(encies 0ith similar Al-content are f(rther in)estigated 0ith respect to their high
temperat(re phase separation 2eha)ior4 High temperat(re !-ray diffractometry 8HT-;<D9 is
performed for this p(rpose4 'canning electron microscopy 8'M9 is employed to st(dy the
film microstr(ct(re4 The res(lts from the )ario(s techni7(es are com2ined determine the
relation 2et0een microstr(ct(re and high temperat(re phase sta2ility of the Ti
1-x
Al
x
3 films4
%
>
Ti'A('N TERNAR3 S3STEM
Ceramics are an important class of str(ct(ral materials and s(rface coatings, 0hich e!hi2it
high strength to 0eight ratio, high strength at ele)ated temperat(res 8non-softening9, and are
chemically inert to most aggressi)e en)ironments4 Among these ceramic coatings, transition
metal nitrides 8TM-39 are ,no0n for their e!tremely high hardness and the 0ear resistance
H&/I, s(ch as TiAl3, the material in)estigated in present 0or,4
2.1 Ti-Al-N
Titani(m-al(min(m-nitrogen is a 0ell-st(died ternary system from the "C/=Js4 The first
reported phase 0as the Ti
$
Al3 in "C>&, 0hich is characteri5ed 2y the high temperat(re
a2rasion resistance and good thermal-electrical cond(cti)ity H&CI4 A simplified phase diagram
of Ti-Al-3 is sho0n in fig(re $-"4 Depending on the chemical composition, the follo0ing
phases can 2e synthesi5ed* a Pero)s,ite phase Ti
&
Al3 and t0o MA; phase Ti
$
Al3, Ti
K
Al3
&
HK=, K"I4 The metasta2le Ti
1-x
Al
x
3 phase e!ists as the solid sol(tion phase 2et0een its 2inary
co(nter parts Ti3 and Al3, 0here x )aries from 5ero to (nity and stands for the atomic
content of Al34 'ince the idea of synthesi5ing the metasta2le phase 0as to enhance Ti3 for
s(rface protection p(rposes, Ti3 0ill 2e introd(ced first for the readerJs con)enience4
In the large gro(p of hard coating materials, titani(m nitride 8Ti39 is one of the late
disco)ered material as compared to other ceramics s(ch as t(ngsten car2ide 8DC9 and
al(min(m nitride 8Al394 Tho(gh titani(m 0as in fact identified in history from "MC=s, its
red(ction method from the titani(m o!ide 8Ti6
$
9 ores had not 2een fo(nd (ntil early "C==s4
'oon as the element co(ld 2e p(rified, it 2ecame 0idely (sed in the form of alloys, o!ides and
M
nitride coatings4 'ince "C%=s, titani(m nitride coating has 2een massi)ely st(died in academia
and (sed in ind(stry4 The coating 0as mostly synthesi5ed 2y chemical )apor deposition
8C:D9 techni7(es in the 2eginning 2eca(se of 2etter adhesion and 0ear resistance on car2ide
tools, 0hile no0adays it can 2e fa2ricated 2y many different methods, chemically and
physically, 0hich allo0 for a large )ariety in its properties4 :ario(s elements and compo(nds
can 2e added into Ti3 system to enhance specific properties for different operation
conditions, s(ch as TiC3, TiBC3 and Ti6C3 H&, K, &/I4 Titani(m nitride is an option for
electrical contact as 0ell, since it has good corrosion resistance HK$I and 0ear resistance
together 0ith good electrical cond(cti)ity4 In addition, titani(m nitride is (sed as diff(sion
2arrier in microelectronics ind(stry HK&I4
Titani(m nitride has roc,-salt crystal str(ct(re, c-Ti3 8or 3aCl crystal str(ct(re, Fig4 $-$ 8a99,
0ith a mass density of %4KK mg#cm
&
4 As the res(lt of different gro0th methods and operation
conditions, it does not al0ays e!hi2it composition HTiI#H3I e7(al to (nity H&/I, 0hile the
atomic ratio 2et0een titani(m and nitrogen determines the color of titani(m nitride4
'toichiometric titani(m nitride has metallic shiny gold color, 0hich is fa)ora2le to 2e applied
as decorati)e coatings4 It has 2een reported that the color of titani(m coatings is gray 0hen it
s(ffers from nitrogen deficiency4 Dith increasing the nitrogen content, the color 2ecomes pale
and yello0ish, and finally reaches the yello0-gold color as the nitrogen content in the film
close to the titani(m4 6)erstoichiometric nitrogen t(rns the appearance into dar, yello0 and
2ro0n H&/, K%, K>I4 Depending on the HTiI#H3I ratio, the microhardness of titani(m nitride can
/
"igure .>, The simplified ternary phase diagram of Ti-Al-3 ternary system4 Adapted from HK"I4
Ti Al
N
3
2
1
TiN AlN
1 Ti
4
AlN
3
2 Ti
2
AlN
3 Ti
3
AlN
Ti
1-x
Al
x
N
)aries from fe0 h(ndreds to more than $=== ,g#mm
$
8K to more than $= 1Pa9, and a common
Ti3 hard coatings 0ill ha)e the hardness in the range of "%== to $$== ,g#mm
$
8"K to $= 1Pa9
H&/I4
The critical dra02ac, of titani(m nitride is the coating fail(re at the operation temperat(res
higher than %== LC, d(e to the replacement of nitrogen 2y o!ygen on the o(ter most layer4
Tho(gh the o!ygen diff(sion rate is rather slo0 thro(gh the nitride and the o!ide layer, the
large molar )ol(me difference 2et0een these t0o compo(nds introd(ces high stress at the
interface4 As more titani(m nitride gets o!idi5ed and reaches the certain critical point in terms
of the molar )ol(me difference, the titani(m o!ide layer spalls from the coating, and the fresh
titani(m nitride layer remains e!posed to the o!idation en)ironment4 The o!idation-e!pos(re
cycles contin(e and finally the s(2strate is e!posed 0itho(t protection, leading to the tool
fail(re4 The o!idation of titani(m nitride 2ecomes a se)ere pro2lem since temperat(re
increasing d(ring the operation of tools is (s(ally ine)ita2le, and the o!idi5ed coating is
largely softened to less than $== ,g#mm
$
8O $ 1Pa9 HM, &/, KMI4 In order to o)ercome the
o!idation pro2lem, Al 0as added to Ti3 system forming the Ti
1-x
Al
x
3 metasta2le phase4
As e!pected, the addition of al(min(m into titani(m nitride coatings impro)es the high
temperat(re o!idation property of the coatings4 At ele)ated temperat(res, the o!ygen attac,s
and replaces nitrogen 2onds from the s(rface of the film for Ti and Al atoms as 0ell4 The
C
"igure .>. The (nit cell of 8a9 <oc,-salt and 829 He!agonal 0(rt5ite crystal str(ct(res4 Adapted from
HKKI4
3#4 354
o!idi5ed al(min(m has a 0ell-,no0n property to form a )ery densely pac,ed thin al(mina
layer on the s(rface, 0hich is )ery diffic(lt to 2e penetrated 2y o!ygen, i4e4, has )ery lo0
diff(si)ity to o!ygen4 The o(t-diff(sion of nitrogen and the diff(sion of o!ygen are retarded
2y the al(mina layer, and f(rther o!idation of the fresh nitrides can therefore 2e delayed H>,
MI4 The Ti
1-x
Al
x
3 coating has lo0er o!idation rate and hardness red(ction (p to M== LC, 0hich
is a comparati)ely higher operation temperat(re as compared to the Ti3 coating4 Moreo)er, it
has 2een o2ser)ed that the mechanical properties of TiAl3 coatings impro)e drastically along
0ith increasing the Al-content in the film H""I4
Dithin the sol(2ility limit of the solid sol(tion, the metasta2le Ti
1-x
Al
x
3 has the roc,-salt
crystal str(ct(re, denoted as c-Ti
1-x
Al
x
3 8Fig4 $-"9, 0ith the metal 8cation9 sites occ(pied 2y Ti
or Al atoms4 Its sol(2ility limit of Al into the Ti3 system has 2een reported 2y many gro(ps
2y means of e!periments H$$, $>I and calc(lations H$K, $%I, and is generally regarded as x
aro(nd =4%% to =4>% at4 N4 It has also 2een reported 2y Adi2i et al4 H&$I that the gro0th
condition for sp(ttering 2ased P:D processes can affect the sol(2ility limit4 The energy
pro)ided d(ring the gro0th can increase the s(rface mo2ility for the films, and therefore
increase the tendency to decompose the metasta2le phase4 Dhen e!ceeding the sol(2ility
limit, the system lo0ers its free energy 2y phase separating, or decomposing, into c(2ic phase
c-Ti3 P c-Ti
1-x
Al
x
3 8fig4 $-$9 and finally into c-Ti3 and he!agonal phase h-Al3 8to 2e more
specific, it is 0(rt5ite crystal str(ct(re Al3, Fig4 $-$ 82994 The decomposition ca(ses
deterioration of the coatings, 0hich lose protection from o!ygen and has similar 2eha)ior as
p(re Ti3 coatings 0hen (sed at ele)ated temperat(res H$$, K/I4
An age hardening effect of the c-Ti
1-x
Al
x
3 metasta2le phase can 2e o2ser)ed a2o)e M== LC,
0hich is an important and preferred feat(re for a hard coating operated at ele)ated
temperat(re4 A thermal acti)ated phase separation, called spinodal decomposition, ca(ses the
formation of fine Ti- and Al-rich domains 8aro(nd fe0 nanometers in diameter9 distri2(ted
0ithin the matri!4 The domains can 2e considered as c-Ti
1-x
Al
x
3 phase 2(t 0ith lo0 and high
x )al(e respecti)ely, and their lattice are (s(ally perfectly coherent thro(gh the matri!4 The
lattice parameter difference 2et0een Ti3 8a B K4$K$9 and Al3 8a B K4=K%9 in their roc,-salt
c(2ic str(ct(re introd(ces the coherent strains in the lattice, 0or,ing as o2stacles to the
mo)ement of dislocations4 F(rther increase of the temperat(re increases the separation of Ti3
and Al3, i4e4, depletes the Al and Ti from the Ti- and Al-rich domains4 He!agonal phase
h-Al3 starts to n(cleate and gro0 from Al-rich domains 8c-Al39 (ntil all the metasta2le phase
"=
transforms into c-Ti3 and h-Al3 phases4 The hardness and 0ear resistance in this stage
red(ces drastically, leading to the coating fail(re H$&, &&I4
2.2 S6i*(+#l D/$(.6(0i,i(*
The so-called spinodal decomposition is one of the diff(sion controlled contin(o(s phase
transformations 0hich happens 0itho(t n(cleation and gro0th4 It is often called a
thermodynamically spontaneo(s phase transformation process, since the system does not ha)e
a 2arrier of n(cleation to o)ercome4 As soon as the diff(sion is acti)ated 2y heat or other
forms of energy, the atoms spontaneo(sly diff(se Jup-hillJ from lo0er concentration regions to
higher4 This (p-hill diff(sion does not e)en o(t the concentration in the matri!, 2(t locally
forms high concentrate locally and deplete the region near2y 8In different )ie0, the depletion
for one specie means high concentration for other species9, for e!ample high Al and Ti
concentrations in the case of metasta2le Ti
1-x
Al
x
34 .nli,e the high concentration interr(ption
at the 2o(ndaries of n(clei, the spinodal domains are contin(o(s in concentration thro(gh
parent phase4 Therefore, it is hard to define J2o(ndariesJ for spinodal domains 8and the reason
called it domains instead of grains94 The domains can randomly appear and disappear at any
place thro(gh the parent phase, since the concentration and the lattice remain in almost perfect
coherency locally4 This ma,es the prediction and the o2ser)ation of phase transformation
thro(gh spinodal decomposition m(ch more diffic(lt than others H&&I4
An A-B 2inary system is gi)en as an e!ample, 0here its free energy diagram at certain
temperat(re T
0
is sho0n in fig(re $4& 8a9 and the corresponding phase diagram is sho0n in
fig(re $4& 8294 The binodal points a and f defined 2y a tangential line c(tting thro(gh the
lo0est points of the c(r)e, represent the sta2le states at the temperat(re 0ith concentration
2et0een
1
and
!
4 The region 2et0een the 2inodal points is called the miscibilit" gap of the
phase diagram 8the solid c(r)e in fig(re $4& 82994 Any concentration 0ithin this region is
thermodynamically unstable or metastable, and can lo0er the total energy of the system 2y
decomposing into the sta2le phases
1
and
!
thro(gh diff(sion4 Dithin the misci2ility gap, a
region 0ith negati)e c(r)at(re 8 d
$
#/ d
$
$
= 9 in the free energy diagram, as the region
2et0een points 2 and e in fig(re $4& 8a9, is 0here the spinodal decomposition ta,es place4 The
c(r)at(re of the free energy is directly proportional to the inter-diff(sion coefficient of the
elements 8A and B atoms9 0ithin the parent phase, according to the sol(tion of Fic,Js
diff(sion la0s4 The negati)e diff(sion coefficient gi)es the J(p-hillJ diff(sion fl(!es in the
""
calc(lation, 0hich is the sol(tion for spinodal decomposition4 As indicated in fig(re $4& 8a9,
the metasta2le state solid sol(tion 0ith total concentration
0
can lo0er its free energy from
#
0
to #
1
thro(gh phase separation to the states at c and d points4 The spinodal decomposition
0ill contin(e (ntil the concentration mo)ed o(t from the region 2-e4 The energy release from
the spinodal decomposition 0ill help the follo0ing decomposition in the regions a-2 and e-f4
At these regions, phase separation proceeds thro(gh normal n(cleation and gro0th processes,
0hich cons(mes energy to o)ercome the 2arrier for n(cleation H&&I4
"$
"igure .>0 The 8a9 free energy diagram at temperat(re T
0
and 829 phase diagram of an A-B 2inary
system 0ith misci2ility gap4 Adapted from H&&I4
+ F2NDAMENTALS OF T41N F1LM DE,OS1T1ON
Thin films can 2e no0adays synthesi5ed 2y a )ariety of ph"sical %apor deposition 8P:D9
techni7(es4 The principle of P:D is to create )apor from either a solid, or sometimes a li7(id,
so(rce4 The )apor is s(2se7(ently transported onto a s(2strate 0here a film is formed4 The
)apor is either created 2y thermal means or 2y moment(m transfer4 The latter is also ,no0n as
JsputteringJ and is the topic of the ne!t section H"I4
3.1 T1/ S6),,/'i*& P'($/00
The sp(ttering is the process that ca(ses eGection of s(rface atoms 2y 2om2arding this s(rface
0ith energetic species4 A simplified schematic ill(stration of the sp(ttering process is sho0n
in fig(re &4"4 In practice, the s(rface, or the so(rce to eGect atoms, is called the target, 0hile
the energetic species are commonly inert gas 8the sputtering gas9 ions, s(ch as Ar
P
, to red(ce
the reactions 0ith any component in the cham2er4 By applying a negati)e potential on the
cathode, on 0hich the target is mo(nted, the Ar
P
ions are accelerated to0ards the cathode and
sp(tter o(t electrons and target species from the target s(rface4 lectrons emitted from the
s(rface, also ,no0n as secondar" electrons, are repelled from the cathode and generate more
sp(ttering gas ions thro(gh collision e)ents, i4e4,
e

+Ar - Ar
+
+ $e

8&4"9
0hich create a plasma maintaining the density of gas ions4 The eGected target species are
transferred thro(gh the gas phase to 2e deposited on a s(2strate and e)ent(ally form a film4
The ratio that descri2es the n(m2er of eGected target species per impinging ion is called
sputtering "ield and depends on the proGectile energy and the s(rface 2inding energy of the
"&
target material H"I4
In order to red(ce the pro2a2ility for the sp(ttered particles to 2e scattered 2efore reaching the
s(2strate, most sp(ttering depositions are carried o(t in an e)ac(ated cham2er4 The fe0er the
collisions 2efore the emitted target atoms condensate, the higher ,inetic energy can 2e
transported to the s(2strate in the 0ay of energetic 2om2ardment, 0hich allo0s for
modifications of the film properties H", $I4
3.1.1 The Magnetron Sputtering Process
D(e to the high escaping rate of secondary electrons in the sp(ttering process descri2ed in
section &4", 0hich is referred as the diode sputtering, the cathode needs to 2e fed constantly
0ith high )oltages 8in the order of ,:9 (nder high sp(ttering gas press(re to maintain a
constant plasma density4 This res(lts in high energy cons(mption 2y the po0er s(pply, lo0
deposition rate d(e to the high operating press(re, and s(2strate heating 2y energetic electrons
d(e to the high potential at cathode4 In addition, the constant high )oltage ,eeps the cathode
temperat(re high, 0hich red(ces the life-time of cathode and increases the ris, of melting a
solid target4
By placing a set of 0ell-designed permanent magnets 2elo0 the target, the Lorent5 force
"K
"igure 0>, The ill(stration to a simplified sp(ttering process4
S6),,/'i*&
7#0 S)66l2
P).6i*&
S20,/.
T#'&/,
S)50,'#,/
7#0
A,(.0
S6),,/'i*&
S6),,/'/+
P#',i$l/0
El/$,'(*0
D/6(0i,i(*
confines the secondary electrons in the spiral traGectories in the )icinity of the target s(rface,
0hich increases the time 2efore secondary electrons lost to the cham2er and the pro2a2ility to
ioni5e the sp(ttering gas4 In this 0ay, the plasma density can 2e s(stained 2y higher ioni5ation
efficiency and the )oltage applied to the cathode can 2e lo0ered4 This modification of
s(pttering process is ,no0n as magnetron sputtering H"I4
In most cases in magnetron sp(ttering processes, the cathode is s(ppied 0ith a constant
)oltage generating a constant target discharge c(rrent4 This techni7(e is ,no0n as direct
current magnetron sputtering 8dcM'9 and has ser)ed for more than &= years the thin film and
coating ind(stry H", KCI4
3.1.2 The Reactive Sputtering Process
By adding a reacti%e gas 8e4g4 6
$
and 3
$
9 along 0ith sp(ttering gas d(ring sp(ttering
deposition, compo(nd films can 2e synthesi5ed, 0hile the process is referred as the reacti%e
sputtering process4 In a typical reacti)e sp(ttering process, compo(nd molec(les formed on
the target s(rface (pon the presence of reacti)e gas are sp(ttered and transported to the
s(2strate, 0hile the formation of compo(nd molec(les at target s(rface is referred as the
target poisoning4 Depending on the composition of gas atmosphere, the compo(nd co)erage
on the target s(rface, also ,no0n as the degree o& poisoning, can 2e different, 0hich is cr(cial
for film composition and other process characteristics, s(ch as deposition rate and target
)oltage H%=I4
Dhen the target co)erage is lo0, (nderstoichiometry films, i4e4 films 0itho(t s(fficient
incorporation of reacti)e gas atoms, are formed4 This operation region is ,no0n as metallic
mode4 .pon increasing the content of reacti)e gas in the sp(ttering atmosphere, the target
co)erage 2ecomes more prono(nced4 Deposition from a f(lly co)ered target, 0hich is refered
as compound mode, leads to the gro0th of stoichiometric films4 In addition, lo0er deposition
rates are commonly o2ser)ed in the compo(nd mode since the compo(nd (s(ally possesses
lo0er sp(ttering yield as compared to the elemental target4 Change of applied )oltage needed
to maintain the same target po0er or c(rrent is also o2sre)ed, since the emission pro2a2ility
of secondary electrons is different for the compo(nd and the elemental target4 For e!ample,
(pon the poisoning of an Al target 2y nitrogen, the )oltage applied to the target decreases
0hen increasing the nitrogen partial press(re4 The opposite is o2ser)ed for Ti target4 H%=I4
"%
To achie)e the desired stoichiometry and maintain high deposition rate, operation in the
intermediate region 2et0een metallic and compo(nd modes, or the transition 'one, is
re7(ired4 Ho0e)er, in some cases the transition mode is (nsta2le accompanied 2y a hysteresis
in the process parameters4 Typically the transition 5one is more (nsta2le for highly reacti)e
com2inations of targets and reacti)e gases4 For instance in this 0or,, the Al target has a 0ider
transition region as compared to the Ti target4 To o)ercome this pro2lem, a feed2ac, system
can 2e installed to monitor and control the deposition parameters, 0hich helps reaching a
dynamically sta2le operating point in transition mode4Berg et al4 H%=I also proposed se)eral
concepts to sta2ili5e the operating point in reacti)e sp(ttering, s(ch as partial press(re of the
reacti)e gas, the p(mping speed of the system, the target c(rrent and the target si5e4
3.1.3 High Power Impulse Magnetron Sputtering
In con)entional magnetron sp(ttering s(ch as dcM' the electron density 8Q"=
"K
- "=
">
m
&
9 and
th(s the degree of ioni5ation of target species 8less than "= N, mostly ne(trals9 are generally
lo04 Ions of target species generated d(ring deposition are desired d(e to the capa2ility of
controlling their energies and traGectories 2y electric and magnetic fields, 0hich pro)ides
additional means for tailoring film properties4 Applying higher po0er to the target and th(s
increasing the electron density is one sol(tion for dcM' to achie)e higher degrees of
ioni5ation4 Ho0e)er in practice, this path0ay is limited 2y the ma!im(m thermal load that the
target can accomodate H&K, KCI4
A no)el techni7(e( High power impulse magnetron sputtering 8HiPIM'9, alle)iates the
limitations of dcM' 2y pro)iding po0er in the form of p(lses, 0hich is typically operating in
the range of "= H5 to "= ,H5 for fre7(encies 0ith fe0 tens of micro-seconds for the p(lse
0idth4 The lo0 dut" c"cle, 0hich means a lo0 p(lse-on time to p(lse-off time ratio, res(lts in
higher po0er density 8Qfe0 ,Dcm
-$
9 d(ring p(lse-on time 0ith lo0 time-a)erage po0er as
for dcM' 8Qfe0 tens of Dcm
-$
9 that the target and the cooling system can 0ithstand4 Higher
electron density 8Q"=
-"/
m
-&
9 and ioni5ation degree 8(p to /= N for Ti9 0as reported as
compared to dcM'4 Impro)ed thin film properties s(ch as adhesion enhancement, porosity
red(ction, and deposition of (niform films on comple!-shaped s(2strates ha)e 2een reported
H&K, KCI4 In addition the grain refinement has also 2een o2ser)ed in H%"I, as the e)idence to a
more energetic ion 2om2ardment4 For reacti)e HiPIM' processes, the increased po0er
density impro)es the remo)al of compo(nds from target s(rface, 0hich red(ces the hysteresis
">
effects and ma,es operation in transition mode more controlla2le H&K, KC, %$I4
3.2 T1i* Fil. N)$l/#,i(* #*+ 7'(8,1
In thin films gro0n 2y P:D, the film microstr(ct(re largely affects the film f(nctionality4 It is
therefore important to (nderstand the thermodynamics 8energy minimi5ation9 and ,inetics
8diff(sion processes9 d(ring gro0th in order to 2e a2le to tailor film properties4 In the
follo0ing sections, thermodaynamic and ,inetic aspects controlling thin film formation are
2riefly disc(ssed H"I4
According to thermodynamics, the s(rface tension for heterogeneo(s n(cleation process in
P:D need to 2e 2alanced in order to minimi5ed the s(rface energy4 This can 2e
mathematically descri2ed 2y the e!pression,

S)
=
S*
+
*)

cos 0
+
8&4$9
0hich is also ,no0n as Eo(ngJs e7(ation4 The ,
S)
, ,
S*
, and ,
*)
are the s(rface tension for
s(2strate-)apor, s(2strate-film and film-)apor interfaces respecti)ely4 The -
+
is referred as the
0etting angle or contact angle for the gro0ing film on the s(2strate and is sho0n in fig(re
&4$4 Depending on the relations 2et0een the s(rface tension components in 7 8&4$9 the
follo0ing gro0th modes are o2ser)ed H"I4
8"9 Dhen the relation

S)

S*
+
*)
is tr(e, the adatom species has stronger 2onds
0ith the same species and the sol(tions to 7 8&4$9 gi)es a 0etting angle -
+
de)iating
a0ay from = L4 Adatoms gro0 in cl(sters 0ith respect to the 0etting angle, leading to
the gro0th mode referred to as island 8)olmer-+eber9 gro0th4
8$9 6n the other hand, 0hen

S)
>
S*
+
*)
holds, the adatoms tend to 2ond 0ith the
"M
"igure 0>. 'chematic dra0ing of the s(rface tensions 2alanced according to Eo(ngJs e7(ation4
Adapted from H"I4

S!

!"

S"
#
$
S)50,'#,/
Fil.
9#6('
s(2strate s(rface atoms and the sol(tion of 0etting angle to 7 8&4$9 2ecomes close to
= L4 The gro0th in this case spreads layers of adatoms on the s(rface (niformly and is
referred to as la"er 8*ran.-%an der Merwe9 gro0th4
8&9 Besides pre)io(s t0o modes, a special relation is o2ser)ed 0hich increases the 0etting
angle from = L along 0ith the formation of the first fe0 monolayers4 The change in the
0etting angles leads to the layer gro0th only in the 2eginning and the island gro0th
after0ard4 H", %&, %KI4
In P:D the island gro0th is more fre7(ently o2ser)ed res(lting in polycrystalline film
str(ct(res4 Ho0e)er the origin of this gro0th mode is ,inetic 8limited diff(sion9, also ,no0n
o0ing to the non-e7(ili2ri(m characteristic of the gro0th process4 The diff(sion 2eha)ior is
affected 2y deposition parameters s(ch as, the s(2strate temperat(re, deposition rate, energetic
2om2ardment and the presence of imp(rities4 'tr(ct(re 5one models 8'RMJs9 has 2een
proposed to descri2e the infl(ence of the adatom diff(sion on the final str(ct(re as a f(nction
of the homologo(s temperat(re T B T
s
# T
m
, 0here T
s
and T
m
are the s(2strate temperat(re and
the melting temperat(re in +el)in H%K, %%I4
In 'one I 8T S =4$9 the energy pro)ided to the film forming species is not s(fficient to acti)ate
adatom s(rface diff(sion4 Incoming atoms sit at the place 0here they first condense to the
s(rface, 0hich is ,no0n as Jhit-and-stic,J or J2allisticJ gro0th and shado0s the region 2ehind
gro0n str(ct(res4 A poro(s and thin col(mnar str(ct(re 0ith )ery ro(gh s(rface is commonly
"/
"igure 0>0 The ill(stration of 8a9 the island, 829 the layer, and 8c9 the mi!ing gro0th modes4 Adapted
from H"I4
3#4 354 3$4
o2ser)ed in 5one I 8Fig4 &4K9 H%K, %%I4
Dhen the homologo(s temperat(re is increased to the range from =4$ to =4K, s(rface diff(sion
is acti)ated4 The diff(sing adatoms on the s(rface are tend to rest in the plane 0ith lo0er
s(rface energy and therefore these planes gro0 faster and dominate other planes, 0hile grains
0ith the fast gro0ing plane oriented to the so(rce of film forming species can gro0 e)en
faster4 1rains 0itho(t fast gro0ing orientations 0ill 2e interr(pted and o)ergro0n, res(lting
in the :-shaped feat(res in the film4 This microstr(ct(re is referred to as 'one T4 H%K, %%I4
An e)en higher homologo(s temperat(re 8T T =4K9 allo0s for 2(l, diff(sion to occ(rs4 The
smaller grains and the :-shaped feat(res are eliminated 2y the diff(sion, and the grain
2o(ndaries are also straightened4 In addition, )oids are filled in and the ro(gh s(rface d(e to
the facets is flattened4 As the res(lt, the 0ider col(mnar grains 0ith m(ch less porosity in
comparison 0ith 5one I and T are o2ser)ed H%K, %%I4
The 5ones I, T, and II are )alid for metallic elemental films4 Ho0e)er, 0hen imp(rity species
are incorporated, intentionally or non-intentionally, imp(rity phases may 2e segregated at the
grain 2o(ndaries, hindering the crystal gro0th of the film forming species4 This gi)es rise to a
glo2(lar microstr(ct(re in films, and is referred as an addition 'one III, 0here the si5e of
grains depends on s(2strate temperat(re4 'imilar effect can 2e o2ser)ed in films gro0n (nder
ion irradiation 0here energetic species interr(pt crystal gro0th4 A characteristic e!ample is
the 0or, 2y Alami4et al4, 0hich has reported the gro0th of Cr3 film 0ith glo2(lar
microstr(ct(re 2y HiPIM', a techni7(e 0hich is ,no0n to pro)ide high fl(!es of energetic
ions to0ards the gro0ing film H&K, %", %%I4
"C
"igure 0>? 'chematic dra0ing of the microstr(ct(res in 'RM 5one I, 5one T and 5one II films4
Adapted from H%KI4
5on" 1 5on" T 5on" 11
$=
& T41N F1LM ANAL3S1S MET4ODS
4.1 X-R#2 Di::'#$,(./,'2
'ince crystals possess (ni7(e ordered str(ct(res and lattice parameters for each phase,
st(dying their diffraction 2eha)ior is a good 0ay to analy5e the microstr(ct(re and phase
composition of crystalline samples4 Diffraction is an elastic scattering interaction 2et0een
photons and s(rface electrons (pon the impinging of electromagnetic radiation onto a s(rface,
0hich mostly occ(rs 0hen the 0a)elength of incoming 0a)e is in similar length scale 0ith
the periodic str(ct(re of s(rface4 The !-rays 0ith energies in 2et0een & ,e: and / ,e: are
the most s(ita2le for the p(rpose of o2ser)ing the diffraction of crystalline samples, 0hich
ha)e periodicity commonly in the length scale of "=
-"=
m4 In addition, !-ray diffractometry
pro)ides a non-destr(cti)e and relati)ely less preparatory 0ay of phase and str(ct(re analysis
HKKI4
The 2asic principle of !-ray diffractometry is descri2ed 2y the BraggJs diffraction e7(ation for
coherent conditions*
6
"
+ 6
$
= n\ = !d
h.l
cos (
n
!
0
$
) =!d
h.l
sin0
$
4 8K4"9
As sho0n in fig(re K4", 0hen the !-ray 0ith 0a)e length U impinges on the s(rface at an
incidence angle V
$
, the difference in the path length 8/
"
P /
$
9 2et0een the planes 0ith
inter-plane spacing d
h.l
0ill 2e an integer n(m2er of the 0a)elength nU4 The scattering 0ill 2e
coherent as represented 2y the direction of 0a)efronts4 The coherent scattering has higher
intensity as compared to other cases, 0hich is recorded in the intensity-to-recei)ing angle
$"
pattern as a diffraction pea,4 By comparing the position of pea,s 0ith the reference patterns,
the phase composition can 2e in)estigated4 In addition, the pea, 0idth, height, and shift 0ith
respect to the reference can also gi)e information a2o(t the coherent domain si5e 8can 2e
appro!imated grain si5e9, the film thic,ness, the resid(al stress and the preferred orientation
in samples HKKI4
For most la2oratory !-ray diffractometry, copper !-ray so(rces are (sed, 0here the
2ac,gro(nd radiations and characteristic !-rays 2esides C( +W-radiations are a2sor2ed 2y the
Be-0indo0 and the 3i-filter4 The samples are only irradiated 2y C( +W-radiations 0hich ha)e
0a)elength aro(nd "4%K X ha)ing t0o specific emission lines +W
"
and +W
$
0ith slight energy
difference4
$$
"igure ?>, The ill(stration of the BraggJs diffraction condition4 The radiations come from A, 2e
diffracted on crystal s(rface layers B to0ard the direction of C4 Adapted from HKKI4
"igure ?>. The schematic ill(stration of symmetrical and gra5ing incident scanning config(rations4
%
2#
X-'#2
S()'$/
D/,/$,('
S#.6l/
For #%!!"trica( #can#6
; < =
For gra7ing incid"nt #can#6
; < :i>/+ #*&l/
&.1.1 The S'mmetrical -2 (on)iguration
The most commonly (sed method to st(dy phase composition 2y !-ray diffractometry is
thro(gh the symmetrical --$- config(ration4 As sho0n in fig(re4 K4$, the positioning of the
detector is al0ays e7(al to the incident angle4 The diffraction pea,s in this config(ration are
gi)en only 2y the planes 0hich are parallel to the specimen s(rface4 The presence of the
diffraction is largely affected 2y the preferred orientation in the sample HKK, %>I4
&.1.2 The *ra+ing Inci,ence (on)iguration
In the gra5ing incidence config(ration, scanning thro(gh )ario(s $- angles 0ith a fi!ed
gra5ing incident angle 0 8Fig4 K4$9 gi)es information a2o(t grains in different orientations as
compared to the symmetric --$- scan4 F(rthermore the lo0 incident angle increases the
intensity ratio 2et0een film and s(2strate, d(e to a larger sampling )ol(me as sho0n in fig(re
K4&4 In this 0or,, some samples 0ere gro0n on single crystalline 'i 8"==9 s(2strates 0hich
ga)e a strong 'i diffraction pea, at aro(nd >C4"& Y and therefore made the diffraction from the
film diffic(lt to 2e o2ser)ed (sing symmetrical scans4 1ra5ing incidence !-ray diffractometry
81I-;<D9 0as therefore (tili5ed for phase composition analysis4 The 1I-;<D (s(ally has a
lo0er intensity as compared to symmetrical scan, since the recei)ing reflections are a0ay
from the primary 2eam4 Therefore a parallel plate collimator 0ith lo0er ang(lar resol(tion 2(t
higher acceptance angle as compared to slit optics is (s(ally (sed HKK, %>I4
4.2 S$#**i*& El/$,'(* Mi$'(0$(62
The scanning electron microscop" 8'M9 is a tool to analy5e the s(rface topographical,
$&
"igure ?>0 The effect on sampling )ol(me 2y (sing lo0er incident angle 0ith the same 2eam si5e 12
Adapted from H%>I4
%
1
%
2
? %
1
Fil.
S)50,'#,/
- -
compositional and diffraction pattern of organic or inorganic samples4 In 'M shorter
0a)elength of accelerated electrons pro)ide higher resol(tion as compared to the optical
microscopy 86M9 0hich is limited to the edge of )iolet )isi2le light 8 Q&== nm94 Its larger
depth of foc(s 8(p to "=== nm9 is one of the most fa)ora2le feat(re allo0ing &-D images to 2e
)is(ali5ed in the topographic mode4 In addition, most 'M meas(rements are (s(ally easier
in operation and sample preparation as compared to the other electron microscopy techni7(es,
s(ch as transmission electron microscopy 8TM9 and scanning t(nneling microscopy 8'TM9
H%MI4
A typical 'M instr(ment can 2e di)ided into fo(r (nits* an electron emitting and accelerating
(nit 8an electron g(n9, sets of electromagnetic lenses for 2eam foc(sing, electron collectors
8detectors9 and an image processing (nit 8Fig4 K4K94 .pon the impinging of the electron 2eam
onto the sample s(rface, the electrons penetrate into the material forming a pear-shaped
interaction )ol(me, from 0hich electrons and electromagnetic radiations are emitted
8Fig4 K4%94 The incident electrons scattered thro(gh the sample are referred to as
2ac,-scattering electrons 8B'94 The electrons generated as a res(lt of inelastic scattering
interactions of the incident 2eam are referred to as secondary electrons 8'9 and A(ger
electrons 8A9, 0here ' are al0ays dominating A4 The electron yield of the s(rface is
$K
"igure ?>? The ill(stration of a simplified 'M system4 Adapted from H%MI4
D/,/$,(' A.6li:i/'
I.#&/
P'($/00i*&@
Di06l#2i*&
A),(. F//+5#$%@
M#*)#l C(*,'(l
El/$,'(*
E.i,,/'
C(il L/*0
U*i,0
S#.6l/
C(*,'(lli*&
Si&*#l0
P).6i*&
020,/.
greatly affected 2y geometrical and elemental feat(res, s(ch as s(rface inclination and atomic
n(m2er as depicted in fig(re K4> 8a9 and 8294 Here different amo(nt of collected electrons from
different region of the s(rface gi)es rise to a contrast in the res(lting signals, 0hich are
amplified 2y the image processing (nit and gi)e topographical or compositional information
a2o(t the s(rface H%MI4
'M is a po0erf(l instr(ment 0hich is 0idely (sed for compositional mapping, fractography,
$%
"igure ?>/ 'chematic dra0ing of the 'M sampling )ol(me and emissions from the interactions of
incident electrons 0ith target atoms4
S#.6li*&
9(l)./
El/$,'(*
I*$i+/*$/
S#.6l/ S)':#$/
A)&/'
El/$,'(*0
SEA
"SE
P'i.#'2
X-R#20
S/$(*+#'2
X-R#20
"igure ?>@ 'chematic dra0ing of the effects on electron emission from the sample s(rface 0hen
irradiated 2y accelerated electrons in 'M, 0hich depend on 8a9 the geometry of the s(rface and 829
the atomic n(m2er of materials4
Au A(
El/$,'(*
I*$i+/*$/
D/,/$,('
3#4 354
El/$,'(*
I*$i+/*$/
and cross-sectional microstr(ct(re o2ser)ations4 Ho0e)er 'M operations is limited 2y the
cond(cti)ity of the samples, 0here acc(m(lation of charges in sample 2y the incident
electrons may locally repel the incoming electrons res(lting in the lose of s(rface information
H%MI4
4.3 El#0,i$ R/$(il D/,/$,i(* A*#l20i0
3lastic recoil detection anal"sis 8<DA9 is one of the ion 2eam s(rface analysis methods
0hich 0as first demonstrated in "CM/ 2y LJc(yer et al4 and in "CMC 2y Doyle et al4 It is )ery
similar in the detection mechanism to another 0idely (sed ion 2eam techni7(e called
4uther&ord bac.scattering spectroscop" 8<B'94 Both <DA and <B' are )al(a2le techni7(es
to o2tain compositional depth profile of samples4 This is done 2y dra0ing o(t information
from the for0ard and 2ac,-scattered particles, 0hich are eGected from the sample s(rface
(pon the collision 2et0een incident ion 2eam 0ith a gi)en energy and atoms at the s(rface4
The commonly (sed energy of the accelerated ions ranges from h(ndreds of ,e: to tens of
Me: allo0ing for a penetration depth in the order of fe0 to tens of micrometers, 0hich is
(s(ally diffic(lt from an electron 2eam4 <DA is a more po0erf(l tool as compared 0ith
<B' d(e to its light element sensiti)ity 8e4g4 C, 3, 69 and depth resol(tion, 0hich is e)en
poor for <B' 0hen a hea)ier element s(2strate 8e4g4 'i, C(, Fe9 is (sed4 <DA o)ercomes the
dra02ac, 2y employing hea)y ions 8e4g4, A(
"&P
, A(
"%P
, I
MP
9, 0hich enhances the pro2a2ility of
generating recoil e)ents and th(s increases the sensiti)ity H%/I4
In an <DA meas(rement, the accelerated hea)y ions are incident on the s(rface of sample,
0here the 2eam is tilted for a certain angle -
i
from the s(rface normal4 According to the 2asic
physical principles of energy and moment(m conser)ations, the collision e)ent 2et0een a
proGectile and a resting s(rface atom of smaller mass 0ill generate the recoil in for0ard
direction 0ith its recoil angle 5 from the incident direction4 .pon the collision, the energy of
the recoil 3
r
is go)erned 2y the energy of incident 2eam 3
p
3
r
= .3
p
8K4K9
2y the ,inematic factor .
. =
Km
p
m
r
cos
$
(0
s
)
m
p
+ m
r
$
4 8K4$9
The m
p
and m
r
are mass of the incident ion and the recoil, 0hile -
s
is the scattering angle of
$>
the primary 2eam, as sho0n in fig(re K4&4"4 The scattered ions from the primary 2eam are
pre)ented to enter the detector 2y p(tting the detector a0ay from the scattering angle, and 2y
inserting a stopping foil in front of the detector, 0hich only allo0s light elements to pass
thro(gh4 The o(tp(t energy spectra collected from the detector can 2e con)erted into the
concentration depth profile for the sample 2y ta,ing different energy loss for recoils coming
from different depths i to acco(nt H%/I4
In this 0or,, <DA 0as (sed for e!tracting the atomic ratio 2et0een titani(m, al(min(m, and
nitrogen in the films4 6!ygen data 0as also an rather important indicator for the porosity in
the coatings, 0hile the a2sence of fl(ct(ations in the composition depth profile ga)e
information a2o(t the sta2ility of the deposition process4
$M
"igure ?>A 'chematic dra0ing of the generation of recoil (pon the impinging of energetic ion to a
resting s(rface atom4 Adapted from H%/I4
#
i
#
s
.
1ncid"nt S*"ci"#
8)
p
9 m
p
:
Sa!*(" Sur/ac"
1ncid"nt ,(an"
R"coi( 8)
r
9 m
r
:
Scatt"r"d 1on
$/
; E.,ER1MENT
In this 0or,, all samples 0ere prepared in the .H: system, named J1inn(ngagapJ, in the
clean room of physics ho(se, Lin,-ping .ni)ersity, 0hich has a cylindrical (pper part,
connected to the transportation cham2er and the main p(mp, and a semispherical lo0er part,
e7(ipped 0ith t0o cathodes, as sho0n in fig(re %4"4 The 2ac,gro(nd press(re 0as in the
range of "=
-/
torr achie)ed 2y a PFIFF< BALR<', TCP &/= t(r2o-molec(lar p(mp in
com2ination 0ith a mem2rane p(mp as a clean forep(mping so(rce4 The press(re in the
cham2er 0as meas(red 2y a BALR<, TP1&== Penning-Pirani m(lti-range ga(ge, 0hich
0or,s from "=
-&
torr do0n to "=
-"=
torr, 0hile d(ring depositions the press(re 0as meas(red
$C
"igure />, A schematic dra0ing of the deposition cham2er operated in this 0or,4
3 7'()*+/+ 4
P).6i*&
S20,/.
N2@A'
7#0 I*l/,
C#,1(+/ C#,1(+/
S)50,'#,/
T#5l/
2y a M+', TEP $M=B signal conditioner connected 0ith a capacitance ga(ge, 0hich 0or,s
in the order of mtorr4 '(2strates 0ere introd(ced into the cham2er thro(gh a load-loc, and a
transportation cham2er, 0hich had their press(re typically in the order of "=
-M
and "=
-/
mtorr4
The s(2strate holder in the main cham2er 0as placed at the confocal point of the t0o cathodes
at a target-to-s(2strate distance of appro!imately "& cm4
Before depositions, all s(2strates 0ere cleaned in (ltasonic 2ath of acetone for % min(tes and
then of isopropanol for another % min(tes4 The films 0ere gro0n 2y reacti)e co-sp(ttering
carried o(t 2y the cathodes, 0here the targets 0ere t0o $ inch Ti and Al targets 8QCC4C% N
p(rity94 The cathode e7(ipped 0ith Ti target 0as operated 2y HiPIM' (sing a MLC, 'PI+
"=== A p(lsing (nit fed 2y an AD:A3CD 3<1E, MD; PI33ACL dc-generator4 It is
,no0n that in HiPIM', target )oltage and c(rrent are time-dependent 7(antities4 These
7(antities 0ere meas(red 2y a CHA.:I3 A<36.;, C">= c(rrent clamp attached to a
homemade )oltage di)ider, 0hich allo0ed for an o(tp(t of the same )oltage to the cathode4
The c(rrent clamp and the )oltage di)ider 0ere connected to a T+T<63I;, TD' %$=C
oscilloscope 0hich monitored the a2o)e 7(antities d(ring depositions4 The The Al cathode
0as operated in dc-mode 2y an AD:A3CD 3<1E, MD; "+ po0er s(pply4 D(ring
depositions, reacti)e gas 3
$
and sp(ttering gas Ar 0ere s(pplied to the cham2er 2y a M+',
M(lti 1as Controller >KM B 0hich allo0s for ma!im(m flo0 of "== 'CCM for each gas
channel4 The s(2strate ta2le 0as rotated at constant speed of "$= <PM d(ring gro0th in order
to ha)e 2etter compositional homogeneity thro(gh the films4
:ario(s fre7(encies 0ere (sed on the HiPIM' cathode to change the degrees of ioni5ation and
therefore the energetic 2om2ardment, leading to the alternation in the film properties4 Prior to
deposition, the change of applied )oltage along 0ith increasing nitrogen s(pply for each
&=
Table />, Ta2le of samples in set " and their corresponding deposition parameters4
3o4 Ti Target Al Target 1as Flo0 Deposition
Time
8min49
Fre7(ency
8H59
P(lse-
Didth 8Zs9
A)g4
Po0er 8D9
Const4
Po0er 8D9
Ar
8'CCM9
3
$
8'CCM9
"-" $=== %= "$= = C= % &=
"-$ %== %= ">= = C= % &=
"-& $%= %= $$= = C= % &=
"-K $=== %= "$= = C= $= &=
"-% $=== %= "$= = C= &= &=
0or,ing fre7(ency 0as recorded to determine the 0or,ing point and the 2eha)ior of target
poisoning4 6perating in metallic mode 0as a)oided 0ithin all depositions in order not to ha)e
elemental Ti and Al atoms in films4
In sample set ", the Ti3 films 0ere deposited to in)estigate the stoichiometry of each
condition and the deposition parameters are sho0n in ta2le %4"4 T0o additional $=== H5
samples 8"-K and "-%9 0ere made to st(dy the effect on the stoichiometry 0ith )aried nitrogen
s(pply4 The stoichiometry of Ti3 films 0as determined 2y )is(al inspection, as mentioned in
section $4"4 Different Ti po0ers 0ere (sed in order to ma,e the deposition rate and therefore
the film thic,ness thro(gh different conditions more similar, 0hich typically decreases 0hen
lo0ering the HiPIM' fre7(ency4
In sample set $, the TiAl3 films 0ere gro0n to st(dy the phase composition and crystal
str(ct(re for )aried Al-content in each condition4 The films 0ere prepared 0ith constant Ti
po0er and nitrogen flo0, 0hile the Al po0er 0as )aried in coarse steps 8 [ % 'CCM 94 The
&"
Table />. Ta2le of samples in set $ and their corresponding deposition parameters4
3o4 Ti Target Al Target 1as Flo0 Deposition
Time
8min49
Fre7(ency
8H59
P(lse-
Didth 8Zs9
A)g4
Po0er 8D9
Const4
Po0er 8D9
Ar
8'CCM9
3
$
8'CCM9
$-" $=== %= "$= = C= % &=
$-$ $=== %= "$= $= C= % &=
$-& $=== %= "$= K= C= % &=
$-K $=== %= "$= >= C= % &=
$-% $=== %= "$= >% C= % &=
$-> $=== %= "$= M% C= % &=
$-M %== %= ">= = C= % &=
$-/ %== %= ">= $% C= % &=
$-C %== %= ">= &% C= % &=
$-"= %== %= ">= K= C= % &=
$-"" %== %= ">= %= C= % &=
$-"$ $%= %= $$= = C= % &=
$-"& $%= %= $$= $% C= % &=
$-"K $%= %= $$= &$ C= % &=
$-"% $%= %= $$= K= C= % &=
$-"> $%= %= $$= %= C= % &=
deposition parameters are gi)en in ta2le %4$4 The st(dy of film phase composition and crystal
str(ct(re 0ere achie)ed 2y a PHILLIP', ;JPert !-ray diffractometer operating in the 1I-;<D
config(ration 0ith the incident angle at & L4 Transitions from solid sol(tion phase to separated
phase in the samples 0ere also identified from the diffraction patterns4
Based on the res(lts of set $, the set & of TiAl3 samples 0ere deposited to st(dy the chemical
composition close to the sol(2ility limit4 The Ti po0er and nitrogen s(pply 0ere ,ept fi!ed
and the Al po0er 0as )aried in finer steps as compared to set $4 The deposition parameters for
set & are listed in ta2le %4&4 The sol(2ility limit of each fre7(ency 0as determined 2y the
presence of identifia2le h-Al3 diffraction pea,4 <DA meas(rements 0ere employed to
identify the Ti-to-Al and nitrogen-to-metal atomic ratio, as 0ell as the o!ygen content in
films4 These detection in <DA 0as carried o(t 2y isotope ions of iodine 8
"$M
I
MP
9 0hich 0ere
accelerated to &= Me: and impinged on the sample s(rface at the incident angle -
i
B $K L,
0hile the recoil angle 0as fi!ed at K% L4 The program (sed to e)al(ate the final composition
data 0as Con)ersion of Time-nergy 'pectra 8C63T', a program for <DA data Analysis9
programmed 2y M4'4 \anson, .ppsala .ni)ersity, $==K4
In sample set K, the TiAl3 films 0ith appro!imately %=*%= Ti-to-Al ratio 0ere deposited to
o2ser)e the microstr(ct(re and to in)estigate the transformation of phases at ele)ated
temperat(res4 The deposition parameters are gi)en in ta2le %4K4 The Al po0ers 0ere )aried for
different fre7(encies to ha)e the desired composition, 0hich 0as o2tained 2y linearly
&$
Table />0 Ta2le of samples in set & and their corresponding deposition parameters4
3o4 Ti Target Al Target 1as Flo0 Deposition
Time
8min49
Fre7(ency
8H59
P(lse-
Didth 8Zs9
A)g4
Po0er 8D9
Const4
Po0er 8D9
Ar
8'CCM9
3
$
8'CCM9
&-" $=== %= "$= = C= % &=
&-$ $=== %= "$= M= C= % &=
&-& $=== %= "$= M% C= % &=
&-K %== %= ">= = C= % &=
&-% %== %= ">= K/ C= % &=
&-> %== %= ">= %= C= % &=
&-M $%= %= $$= = C= % &=
&-/ $%= %= $$= &$ C= % &=
&-C $%= %= $$= &% C= % &=
e!trapolating the Al po0er 0ith respect to the chemical composition data of sample set &4
Different deposition times 0ere (sed in order to achie)e similar film thic,ness, ma,ing the
res(lts more compara2le4 The $=== H5 condition 0as e!cl(ded from set K 2eca(se of its high
o!ygen content determined 2y <DA, 0hich may change the phase composition in the film4
The microstr(ct(re of sample set K 0as o2ser)ed from cross-sectional images ta,en 2y a L6
"%%= 1emini 'M 0ith the electron 2eam accelerated to % ,e:4 HT-;<D 0as (sed to st(dy
the phase composition and decomposition 2eha)ior at ele)ated temperat(re achie)ing 2y a
PHILLIP', ;JPert !-ray diffractometer4 D(ring HT-;<D meas(rements, the samples 0ere
inserted in an e)ac(ated cham2er 8Q"=
-%
m2ar9 and heated (p in the step of "%= L from M== to
""%= LC 2y Ta filaments4 'cans 0ere made at each temperat(re after holding for &= min(tes
and at am2ient temperat(re, 0here one e!tra scan 0as made for samples at ""%= LC after
holding for e!tra & ho(rs4
In this 0or,, "/]"/ mm single crystalline silicon s(2strates 0ith polished 8"==9 s(rface 0ere
(sed in the depositions of sample sets " to &4 In set K, single crystalline 'i and poly crystalline
Ta s(2strates 8"=]"= mm9 0ere (sed for different meas(rements4 The single crystalline 'i
s(2strate is 2eneficial to 'M cross-sectional o2ser)ations since it can 2e clea)ed easily and
perfectly, 0hile the Ta s(2strate is less reacti)e 0ith the TiAl3 film in their interfaces at
ele)ated temperat(res (sed in HT-;<D as compared to 'i4
&&
Table />? Ta2le of samples in set K and their corresponding deposition parameters4
3o4 Ti Target Al Target 1as Flo0 Deposition
Time
8min49
Fre7(ency
8H59
P(lse-
Didth 8Zs9
A)g4
Po0er 8D9
Const4
Po0er 8D9
Ar
8'CCM9
3
$
8'CCM9
K-" %== %= ">= &C C= % "%=
K-$ $%= %= $$= $C C= % $K=
&K
0 RES2LTS AND D1SC2SS1ON
The ;<D patterns recorded from samples 0ithin set $ 0ith p(lsing fre7(encies of $=== H5,
%== H5 and $%= H5 are sho0n in fig(re >4" 8a9, 829, and 8c9 respecti)ely4 The dotted lines
indicate the pea, position of 2(l, (nstrained c-Ti3, c-Al3, and h-Al3 H%CI4 In the diffraction
patterns corresponding to p(re Ti3 films, i4e4 films gro0n at an Al po0er e7(al to 5ero, one
pea, 0ith strong diffraction intensity and the other 0ith relati)ely 0ea,er intensity can 2e
o2ser)ed at appro!imately &>4% L and K$4% L4 These pea,s can 2e attri2(ted to the Ti3 8"""9
and 8$==9 pea,s4 The Ti3 8"""9 pea,s in fig(re >4" 829 and 8c9 are fo(nd left-shift 0ith respect
to the 8"""9 pea, position of the reference, 0hich is not the case for the 8"""9 pea, in fig(re
>4" 8a94 In general, the pea, position in ;<D patterns is determined 2y the si5e 8or inter-plane
spacing9 of the lattice contri2(ting to the reflection as gi)en in g4 8&4"9, 0hich is therefore
affected 2y resid(al strain and chemical composition of the lattice4 The res(lts o2tained here
0ill 2e disc(ssed later in the present section after presenting the chemical composition data4
It is also o2ser)ed that the intensity of the Ti3 8"""9 pea, decreases 0ith red(cing the p(lsing
fre7(ency, 0hile the pea, 2ecomes 2roaden at the same time4 The pea, height 8intensity9 and
0idth are in general determined 2y the coherent domain si5e 8in proportional to the grain si5e9
and the film thic,ness4 'ince the thic,nesses of the films in set $ are not the same, the
disc(ssion of these differences is postponed for the samples in set K, 0here the films of
similar thic,nesses 0ere deposited4
.pon increasing po0er applied to the Al target, right-shift of the 8"""9 as 0ell as the 8$==9
pea, can 2e seen4 As mentioned a2o)e that increase of diffraction angle means the decrease in
the lattice si5e4 According to the 0or, 2y Adi2i et al4 H>=I, the decrease of the lattice si5e
&%
&>
"igure @>, The 1I-;<D spectra of TiAl3 films deposited 0ith 8a9 $=== H5, 829 %== H5 and 8c9 $%=
H5 HiPIM' fre7(encies on Ti target and )ariant DCM' po0er on the Al target4
&M
"igure @>, 8d9 The 8"""9 pea, positions of the metasta2le phase 0ith respect to 1I-;<D spectra in
fig(re >4" 8a9, 829, and 8c94
indicates that Al atoms are incorporated into the Ti3 lattice forming the c(2ic metasta2le
phase 8c-Ti
1-x
Al
x
394 The reason is that c-Al3 has smaller lattice in comparison to c-Ti3
res(lting in the shrin,age of the a)erage lattice si5e 0ith respect to Ti34
The ang(lar position of the 8"""9 pea, as a f(nction of the po0er applied on the Al target is
plotted in fig(re >4" 8d94 It is o2ser)ed that the change of the pea, position is marginal a2o)e a
certain po0er limit4 This limit is appro!imate K=, &M, and &$ D for samples gro0n at a
p(lsing fre7(ency of $===, %==, and $%= H5, respecti)ely4 This 2eha)ior indicates the
sat(ration of the metal s(2lattice 0ith respect to the Al incorporation4 In addition for the
po0er a2o)e this limit 8M%, %=, K= D for $===, %==, $%= H59, intensity ma!ima at Q&& L for
$=== and %== H5 and at Q&% L for $%= H5 appears, 0hich can 2e assigned to the h-Al3 pea,s4
At the same time, the intensity of the c-Ti
1-x
Al
x
3 8"""9 pea, decreases significantly4 These
facts indicate that samples gro0n at these conditions ha)e 2een decomposed into the sta2le
h-Al3 and c-Ti3 phases4
The composition res(lts from <DA are listed in ta2le >4"4 An (nderstoichiometry in terms of
3 contents can 2e o2ser)ed from the films gro0n at $=== H5, 0hich is not the case for the
films gro0n at %== and $%= H54 These res(lts are consistent 0ith the color of the
corresponding Ti3 samples in set " 8Fig >4$94 The sample gro0n at %== and $%= H5 e!hi2it
golden-li,e color 0hile the film deposited at $=== H5 has a gray-li,e appearance4 It is 0orth
mention that the color of the samples gro0n at the p(lsing fre7(ency of $=== H5 remained
&/
Table @>, Ta2le of the <DA res(lts from set & samples4
3o4
Al Target Composition 8at4 ratio9
Po0er 8D9 HAlI # HTiPAlI H3I # HTiPAlI 6!ygen 8at4 N9
&-" = = =4/C $"
&-$ M= =4>/ =4/% "%
&-& M% =4M= =4/% "M
&-K = = =4C> "K
&-% K/ =4>$ =4C> "$
&-> %= =4>K =4C> "$
&-M = = "4"& ""
&-/ &$ =4%M "4== "=
&-C &% =4>" "4== "=
grey 8sample "-K and "-%9 e)en 0hen the nitrogen s(pply d(ring deposition increased4 This is
in contrast 0ith the res(lts from 'pro(l et4 al4 H>"I, 0hich ha)e sho0n an increase of nitrogen
incorporation in Ti3 films from =4M= to "4=" 8H3I#HTiI ratio9 2y increasing nitrogen partial
press(re d(ring depositions4 This 2eha)ior can 2e e!plained 2y the res(lts from :as( et al4
H>$I 0hich ha)e reported that the H3I#HTiI ratio increased from =4&/ to "4" as the temperat(re
of s(2strate heating d(ring depositions changed from Q$% to %== LC4 In o(r case, the films
0ere deposited at relati)ely long target-to-s(2strate distance 0ith small cathode diameters,
0hich led to small thermal load from the plasma4 Tho(gh 0e are not in the position to
confirm the reason for the stoichiometric Ti3 films deposited 0ith p(lsing fre7(encies of %==
and $%= H5, 0e s(ggest t0o e!planations for this 2eha)ior*
8"9 The higher plasma density generated (pon decreasing HiPIM' fre7(encies is a2le to
dissociate larger amo(nt of nitrogen molec(les 83
$
9 into mono-atoms and ions 83 or
3
P
9, 0hich are typically more reacti)e than molec(lar form4 The increasing of
dissociated species can poison the target more completely, and also increase the
reaction 2et0een the elemental species on the s(2strate side4
8$9 The higher potential applied to the cathode d(ring the p(lse-on time of lo0er HiPIM'
d(ty-cycle is a2le to accelerate the electrons to higher energy to0ards the s(2strate4
Dhen the energetic electrons impinge on the s(2strate, the s(2strate is heated 0hich
impro)es the nitrogen incorporation as descri2ed a2o)e4
6 content of samples in set & is also listed in ta2le >4"4 It sho0s that the 6 content red(ces
0ith decreasing the p(lsing fre7(ency4 This 2eha)ior can 2e e!plained 2y the enhanced
energetic 2om2ardment created (pon decreasing the HiPIM' p(lsing fre7(ency, as descri2ed
in section &4"4&4 Denser str(ct(re in films can therefore 2e deposited 0ith assisted 2y this
&C
"igure @>. Pict(re of the Ti3 samples, 0hich from left to right are $%=, %==, and $=== H54 The
regions 0ith relati)ely 2right color on the film s(rface are remo)ed in <DA meas(rements4
enhanced 2om2ardment, 0hich pre)ents post-deposition 6 incorporation4 In addition, the 6
detected in films is not incorporated d(ring deposition since the same press(re 0as (sed
thro(gh all depositions of samples in set &4 The same press(re in the cham2er gi)es similar
formation time of 6 monolayer d(ring deposition, 0hich means that the n(m2er of 6 atoms
incorporated in films is fe0er 0ith higher deposition rate4 De sho0 later in the section that
the deposition rate decreases 0ith the p(lsing fre7(ency4 Along 0ith the increase of 6 content
0ith increasing the fre7(ency indicates the incorporation of o!ygen sho(ld ta,e place at the
other time than d(ring deposition4
The left-shift of Ti3 8"""9 pea, o2ser)ed in fig(re >4" 829 and 8c9 as compared to
fig(re >4" 8a9 can partly 2e e!plained 2y the amo(nt of o!ygen incorporated into the c-Ti3
lattice4 The c-Ti6 has shorter lattice constant as compared to c-Ti3 8K4"M and K4$K X for
c-Ti6 and c-Ti39, 0hich shrin,s the a)erage lattice si5e in the same 0ay as c-Al3
incorporates into c-Ti34 This shrin,age of c-Ti3 lattice can shift the 8"""9 pea, position to the
right in the angle of Q=4>& L, calc(lated 2y inserting the lattice constants a2o)e into 74 8&4"94
Ho0e)er since the diffraction pea, of c-Ti6 is not o2ser)ed in the ;<D patterns, there sho(ld
not 2e significant amo(nt of 6 incorporate into c-Ti3 lattice forming c-Ti64 Therefore, the
pea, position sho(ld 2e less affected 2y the 6 content in films4
From the Ti-to-Al atomic ratio, a red(ction of the sol(2ility limit (pon decreasing the p(lsing
fre7(ency is o2ser)ed4 According to Adi2i et al4 H&$I the limited s(rface mo2ility can sta2ili5e
the metasta2le phase 0ith higher incorporated c-Al34 In o(r case, this indicates that the lo0er
p(lsing fre7(ency, the higher s(rface mo2ility is pro)ided to gro0ing films4 The higher
s(rface mo2ility can either 2e pro)ided 2y the electron introd(ced s(2strate heating as
mentioned a2o)e, or 2y the moment(m transferred from the energetic 2om2ardment4
The 'M images for set K samples are sho0n in fig(re >4& 8a9 and 829, 0hich ha)e thic,nesses
aro(nd C&= and />= nm respecti)ely4 In com2ination 0ith the deposition time listed in ta2le
%4K, deposition rates of >4$= and &4%/ nm#min can 2e calc(lated, 0hich sho0s a red(ction
aro(nd K$ N 0hen lo0ering the d(ty-cycle of HiPIM'4 Ho0e)er a possi2le different
deposition rate from Al cathode also needs to 2e considered, 0hich is introd(ced 2y )aried Al
po0er (sed in the samples4
In addition, no apparent difference in the microstr(ct(re is o2ser)ed from the 'M image4 A
transition to a more gran(lar str(ct(re 2y increasing pea, c(rrent as reported 2y Alami et al4
K=
K"
BaC
BbC
"igure @>0 The 'M cross-sectional images of TiAl3 samples deposited 0ith 8a9 %== H5 and 829
$%= H5 HiPIM' fre7(encies4 Both images 0ere ta,en (nder magnit(de of "%=,=== ;4
K$
"igure @>? The HT-;<D spectra of TiAl3 films deposited 0ith 8a9 %== H5, and 829 $%= H5 HiPIM'
fre7(encies4 The s(2strate pea, is la2eled 0ith J'J at the 2ottom of 2oth diagrams4
H%"I is not o2ser)ed in o(r 0or, as the p(lsing fre7(ency changed from %== to $%= H54 In
com2ination 0ith the 6 content listed in ta2le >4", 0e s(ggest that there is a minor change of
the microstr(ct(re 0hich is 2eyond the resol(tion of the analytic method 8'M9 that 0e (sed
in this 0or,4 6n the other hand, the change of energetic 2om2ardment 2y )arying the p(lsing
fre7(ency from %== to $%= H5 is pro2a2ly not large eno(gh to ma,e significant change in
microstr(ct(re that is detecta2le for the resol(tion of 'M4
The HT-;<D diffraction patterns of samples in set K are sho0n in fig(re >4K 8a9 for %== H5
and 829 for $%= H54 <eference scan 0as made for the Ta s(2strate, 0hich is inserted at the
2ottom of each fig(re and la2eled 0ith JTa s(24J4 In addition, the only diffraction pea,
contri2(ted 2y the s(2strate in the scanned region is at &/4KM L according to the po0der
diffraction reference of Ta and is la2eled 0ith an J'J 2elo0 !-a!is for 2oth fig(res H>&I4 It is
o2ser)ed that the intensity of Ta s(2strate decreases at ele)ated temperat(re and increases
after0ards4 This change of intensity means that the grain si5e of Ta s(2strate )aries (pon
heating4 The grain si5e changes 2eca(se the Ta 0as annealed in the temperat(re 0e (sed,
0hich red(ces and regains intensity 0hen the Ta recrystalli5es and gro0th again4
'ince samples in set K 0ere deposited into similar thic,nesses and chemical compositions, the
comparison of their ;<D patterns is more straight for0ard4 In the ;<D patterns of the as
deposited films 8la2elled Jas dep4J9, the left-shift of the 8"""9 pea, is more prono(nced for the
sample gro0n 0ith p(lsing fre7(ency of $%= H54 This o2ser)ation is consistent 0ith the
notion that an increase of HiPIM' p(lsing fre7(ency generates more intense energetic
2om2ardment on the gro0ing film4 It is ,no0n that the energetic 2om2ardment introd(ces
particle implantation into the film, 0hich e!pands the lattice si5e of the gro0ing species4
Dhen the 2om2ardment is enhanced, more ions are implanted into the film leading to a larger
e!pansion of lattice and therefore more prono(nced left shift in diffraction pea,4 In addition, a
similar pea, shape 8height and 0idth9 is o2ser)ed from the ;<D patterns of as deposited
samples4 'ince the samples are ali,e in thic,ness, the high resem2lance in the pea, shape
means there is no m(ch difference in the grain si5e as 0ell as the microstr(ct(re4 This
o2ser)ation is also confirmed 2y the 'M images 0itho(t significant difference in the
microstr(ct(re sho0ed in fig(re >4& earlier in this section4
.pon the heating process of 2oth samples, rela!ations of 8"""9 pea, are o2ser)ed at M== LC as
the pea, shifted to higher diffraction angle, 0hich releases some of the resid(al strain ind(ced
K&
2y the sp(ttering process4 Mean0hile, the 8"""9 pea, 2roadening at M== LC indicates the initial
stage of spinodal decomposition, 0hich forms the coherent c-Al3 domains o(t from the
parent phase4 These domains gro0 in n(m2er faster than in their si5e, 0hich destr(cti)ely
interfere the reflections from the c(2ic metasta2le phase and therefore the 8"""9 pea, red(ce
in intensity and di)erse in 0idth4 At "=== LC the film pea, for 2oth conditions slightly mo)es
2ac, to left, indicating the depletion of Al3 in the parent phase4 At the same time the depleted
metasta2le phase starts to gro0 fine Ti3 grains, 0hich gi)es rise to a 2road Ti3 pea,4
As the temperat(re ele)ated to ""%= LC, the 8"""9 film pea, for 2oth conditions )anishes
completely and the Ti3 8"""9 pea, contin(es to gro0 in intensity, 0hich indicate the
e!ha(stion of the parent phase and the increasing grain si5e of Ti3 phase4 The h-Al3 grains
start to gro0 in si5e and their reflections arise at &K L and &>4% L4 In addition, the reflections
from r(tile 8Ti6
$
9 phase
"
0ere o2ser)ed at Q&> L meaning a detecta2le amo(nt of titani(m
had 2een o!idi5ed d(ring the heat treatment4
After holding at ""%= LC for & ho(rs, the %== H5 sample sho0s higher intensity for 2oth
h-Al3 pea,s than the $%= H5 sample, 0hile the r(tile phase also had higher reflection
intensity for the first 8Q&> L9 and the second 8Q&C L9 pea,s in the %== H5 sample4 The larger
coherent domain si5e of h-Al3 and r(tile phases may indicate that the %== H5 sample is more
fa)ora2le for grain gro0th4 'ince the grain gro0th is also a diff(sion controlled process, the
%== H5 sample sho0s an open str(ct(re in terms of diff(sion 0hich is pro2a2ly more poro(s
as compared to the $%= H5 sample4 Tho(gh the difference is (ndetecta2le from 'M images,
the o!ygen contents sho0n in ta2le >4" agree 0ith the res(lts from HT-;<D4 Dhen the
operation fre7(ency of HiPIM' is lo0er, the films 2ecome denser 0hich pre)ent o!ygen
incorporation and retard gro0th processes4
" There are se)eral polymorphs for titani(m dio!ide 8Ti6
$
9, and three of them can 2e fo(nd in nat(re*
the metasta2le phase anatase, 2roo,ite, and the sta2le phase r(tile4 <(tile is one of the most sta2le
phase for Ti6
$
0ithin all temperat(re range, and therefore it 0as challenging to red(ce p(re Ti in
history H&I4
KK
) S2MMAR3 AND F2T2RE O2TLOOK
In this 0or,, 0e see, for the feasi2ility of controlling the phase sta2ility Ti
1-x
Al
x
3 metasta2le
phase at ele)ated temperat(res thro(gh modification of microstr(ct(re in films4 De deposited
thin film samples 2y reacti)e co-sp(ttering 0ith t0o cathodes4 The cathode connected to a
HiPIM' po0er s(pply 0as e7(ipped 0ith a Ti target, 0hile the other cathode operated 2y a
direct c(rrent po0er s(pply 0as e7(ipped 0ith an Al target4 :ario(s p(lsing fre7(encies 0ere
(sed to change the microstr(ct(re and altered po0er on Al target 0as t(ned to achie)e
different Al content in films4 Films 0ere first deposited to 7(alitati)ely in)estigate their phase
composition achie)ed 2y 1I-;<D, and then e!tra films 0ere prepared for analy5ing
7(antitati)ely chemical composition 2y <DA4 Based on the res(lts from 1I-;<D and
<DA, samples 0ith desired phase and composition 0ere gro0n4 Microstr(ct(res of last
samples 0ere compared from 'M images, 0hich 0ere related to their phase transition
2eha)ior at ele)ated temperat(res st(died 2y HT-;<D4
De o2ser)ed the start and sat(ration of 8"""9 pea, right-shift in 1I-;<D patterns along 0ith
increasing the Al cathode po0er4 This is d(e to the incorporation and sat(ration of Al atom in
Ti3 lattice4 The h-Al3 pea,s 0ere also o2ser)ed soon after the decomposition of the
metasta2le phase4 In the res(lts of <DA, the Al sol(2ility limit 0as fo(nd to decrease 0ith
red(cing the p(lsing fre7(ency, indicating that higher energy 0as pro)ided to gro0ing films
at lo0er fre7(ency4 Moreo)er, a red(ction of 6 content 0as also o2ser)ed 0hen decreasing
p(lsing fre7(encies, meaning that denser films 0as deposited 0hen the fre7(ency 0as lo0er4
Larger grain si5e 8appro!imated from the diffraction pea, intensity9 0ere determined from the
HT-;<D patterns of the sample deposited 0ith higher HiPIM' fre7(ency4 The red(ction in
K%
grain si5e indicates the diff(sion controlled grain gro0th 0as more retarded in $%= H5 sample
as compared to %== H54 De s(ggested that a denser film 0hich is more diffic(lt to acti)ate
diff(sion processes 0as deposited 2y lo0er HiPIM' p(lsing fre7(ency4 .nfort(nately that the
relation 2et0een the microstr(ct(re and the diff(sion 2eha)ior of Ti
1-x
Al
x
3 films 0as not f(lly
esta2lished4 'ince the )ariation in deposition parameters (sed 0ere not large eno(gh to ha)e
apparent transition in the microstr(ct(re, 0e 0ere not a2le to compare the difference 2et0een
samples o2ser)ed 2y 'M4 Ho0e)er the o2ser)ations from HT-;<D patterns can 2e an
important starting point of st(dying the feasi2ility of controlling the diff(sion 2eha)ior 2y
modifying the microstr(ct(re of Ti
1-x
Al
x
3 films4
To contin(e from this point, e!pansion of the deposition parameter space, s(ch as higher
fre7(encies or longer p(lse-0idths, is needed to ma,e more compara2le difference in terms of
the microstr(ct(re4 De can also apply the s(2strate heating or 2ias )oltage to eliminate the 6
incorporation in samples4 6n the other hand, thermal analysis 8TA9 and heat flo0 analysis can
also 2e employed to determine the direction of heat flo0 as 0ell as the amo(nt of enthalpy
d(ring the decomposition e)ents of TiAl3 system at ele)ated temperat(res4 The res(lts from
TA and calorimetry can 2e informati)e to dra0 o(t concl(sions of the tendency of phase
transformation and therefore the diff(sion 2eha)ior4
In addition, 0e o2ser)ed the trend of increasing nitrogen incorporation 2y lo0ering HiPIM'
fre7(encies 0hich led to Ti
1-x
Al
x
3 films 0ith desired stoichiometry4 Ho0e)er in this 0or,, 0e
are not a2le to confirm the mechanism of this o2ser)ation4 More detailed st(dies need to 2e
performed to in)estigate the reactions on target s(rface and gro0ing film along 0ith the gas
composition d(ring reacti)e sp(ttering4
K>
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.'A 8"CC"94
H&CI M4D4 Barso(m, D4 Brod,in, T4 l-<aghy, 'cripta Mater4 0@ 8$==&9 %4
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