-. ~,~.

'~.

ELSEVIER Thin S,d id l:illV~.s312 ( Itit)8) 147- 155

Structure of plasma-deposited amorphous hydrogenated boron-c rbon

thin films
A. A n n c n , M. SaIL R. B e c k m a n n , A. yon Keudell, W. Jacob +
.Ah +~. f'h m,'/,- h~.~titut.liir Pht.~o r qdO'.~il,. 1:7 'RA "171,%IA.~.~+,<'i,mm, I 1-$5 74S ( ;,r< hi,t:. (h'rm<mv

Received 25 April 1907: ~,cccplcd 4 August 19t)7

Abstract

Amtu'l~hous hydrogemtled btmm-¢arb~m (a-B~ , C , ' H ) Ihin films ~ere prepared by radit,-t'requency plasma deposititm u.,,ing CH a :rod
B , I-I, diluted in H , as precursor gases. The composititm and density were delcrmined by ion-beum analysis. The densities t}l" the a-B:H
and a-C:H films are similar with tJ m 1.72 '3 cm ~. a v:due typical of hard and dense a-B:H and a-C.H films. Ternary a-B I , C , : t l l'ihlls
are tens dense, having a tninimum dellSily td' i ) ~ 1.48 g e m ~ at x = ().71. Fourier transf~,ln infrared spectrt)sCOlLV was used fur
qualitative and tluantilativc aimlysis ~+I"lilt: bt,ltlillg strticttlrcs. The ploperlies of films up to .x = 1),2 are ctmlpal'ablc It+ tllone of pure
a-B:l-I filtns. Hmvever, small carbon cunlents iulquencc the film slruclurc, mainly reducing the number of B - H - B bridge bonds, which
m'c abttndant in pure a-B:il films, l.mv film densilies at .x-~ 0.5 u} 0.8 ¢orrehtte with the inaxJnRull inlcnsit), of the extrinsic B - C
v i b r a t i t m a l l n o d e ;.il'tRIlld 12011 c i i l I thne It+ ternlitlal - C I I ~ gi'oups, indicating a less cross-linked network structure. Mt~dil'icalions uf the
network arc indicated for .~> 0.7. Bclmv, carbon is predominantly sp ~ hybridised and bonded betxveen buron neighbours. Above x = (1.7
I]le ilelwork i~ecOlneS carbon dolninated with an increasing nulnber of cttrboln-CLll'bt,I bonds i.uld 1.111increusing fl'al.'litln tlf ,,p2 hybridised
till'bOll Wtls ob,,erved. The cxtrinsJ,: B - C vJbrillJon~.ll m o d e at t20ll Ctll i a n d Ihe imt'Jnsic B - C nel~A-ork vibration at 15011 em ~ were
qu:mtified over the whole range el +a-B~ ,C,:H film cnmposilions. The absorption ¢onMalll of the extrinsic B - C vibrational mode at
t20(I em ~ was estimated. ~; 1908 Elsevier Science S.A.

Kevu'ord.w Buron-carl~on lhin film',: Pktsma dcl~mi|ion: hm-t~cam amd)nin

I. Introduction and a - B : H fillns w e r e tile .,,ub.jcct of our previous w o r k

[ 2 0 - 2 2 ] . This p a p e r rcports tile study o f the structure and
A m t w p h o u s h y d r o g e n a t e d boron and earl'urn I'ilms have
propcrtic~ of the ternary alloy a-B t ,C,:tl. For this pur-
been studied in v i e w o f Iheir successful use. for e x a m p l e .
pose, a-B 1 ,(7_,:H filrrls w e r e depc, sitcd by r a d i o - f r e q u e n c y
as protective first-wall coatin~:s in fusion reactors [ I - 4 ] , as
i~htsma c h e m i c a l v a p o u r d e p o s i t i o n ( R F - P C V D ) over the
s c m i c t m d u c t i n g materials [5-71 and for tribological appli-
w h o l e range o f COlllpOsilJOns from pure a - B : H t o p u r e
cations [ 8 - I I ] , E s p e c i a l l y for a-C:H nluch w o r k has been
a - C : H . T h e fihn complexities w a s d c l c r m i n c d by i o n - b e a m
d o n e to clarify the struclure and physical properties [ t 2 - t 4 ]
analysis (IBA). Fourier transl'orrft inl+rared (FTIR) spcc-
its a fuilction o f the d e p o s i t i o n parainetel's. For a - B : t l there
Irosu'opy was upplicd Io investigate the film sll"l.lcltlre ill
are also s o m e studies tm tile structure, m a i n l y r e g a r d i n g
general and especially the question how II.vdrogcn is bonded
the role of hydrogerl b t m d e d to b t m m [ 1 5 - 1 7 ] or impurity
to lilt? different I'~oron and c a r b o n siles, Furlhernlon2, \ i b r a -
incorporation [18,19]. l.css attention has been paid It) tile
liOllS of the B - C ilelWol'k %v~21"~2tile object o f o u r inx cntiga-
gap b e t w e e n these two different a m o r p h o u s h y d r o g e n a t e d
lions. T h e m e c h a n i c a l and tribological properties e l a-
n l a t c r i a l s - - l l l e tern:try alloy t)f anlt)rl~llt)t|s tlyth'ogenaled
B : C : l t films v, e r c r e c c u t h ' investigated and c o m p a r e d v,ilh
borot'a ¢llrbidc (a-B I , ( ' , : f l ) ,
lhe m i c r o s l r u c t u r a l properties an d e l e r m i t l e d bx infrared
The physical fn'opcrties, structure and e r o s i o n o f a-C:H
anti R;|lnan spcctroscofLv [23.24].
Hvdro,,en.e- is of special interest in Ihis nvslClll since
('t~rrcnpt~ntlhlg illtll',t~l'" Tel.: + 4q-Sq-32tJg-2fllS: I'll\: + 40-St} 329q Ii)'th't~gell bolldillg plays a central talc not Olliy for tile
I 149: c-maih jacul~to'ipl~.mpe.de. tltwslitm of inlernal .,,tress,Ol + I'dm ,,Iabilil.\'Ix,z11,but ~dno

()4)41)-hIlt)l)/gX/'$19.(}() ' Iqt)8 t(l',e',iu'u .',k'iencc s;..,\. All righl,, r,.',,cr~,cd.

,"11 ,NI}()4I)-(,()O()( 07 )1}1)735-~)
148
for the erosion nlechai|isnl [2.25-27]. A study of the
erosion of these a-B I ,C,:H films by hydrugen and he-
lium pl:tsm:m is presented elsewhere [28].
in a recent study, yon Keudcll and Jacob [29] showed
that investigations of thin fihus by FTIR spectroscopy grin
be significantly improved by using a new f(wmalisni for
data evaluatii+n. This I'ornlalisnt was denqonstrated to be
advalllageous for inlert)relalion and tluanlJ fication of ;I-(':H
and a-B:H PTIR speclri.i [17,29] and is Lit,~o used for the
FTIR I'ilnl analysis in Set.'lion 2.
2. Experimental procedure
A nu)rphous Ilydrogenated boron-carhor! (a- B I , C , :H )
thin films were prepared by ~.apacitively coupled 13.56
Mltz RF-PCVD. A detailed description of the der~ositiorl
apparatus is given elsewhere {20].
In the present study, the suhstrate temperature Ts and
the self-bias Usf ~ were chosen constant. Applying an RF
power of 50 W to the substrate electrode (100 mm in
diameter), which corresponds to a power density of 0.65
W cm ;, yielded a self-bias voltage of 235 V. The sub-
strate temperature Ts was controlled with a pyrometer. Nu
additional heating was applied and based on our experi-
ments at higher 1~ [17.21] allt] the measured increase of
7".,; with self-bias voltage at higher self-bias w)ltages(up to
350 V). Ts was estimated to be below about 330 K in lhc
present experiments. A mixture of 10~/~ B , H , in I-!, and
CH.~ was used ;is precursor g;l~. Iv) order to adjust the B / C
content, the partial tlows ~q" (B.,H<, + H , ) ( l"n) and CHI
( I ~ . ) were varied I'ronl ()It) I0 seem. with the total gas
Ilow ([~,,i = I ' l l + I t ") kept Or+liSt;lilt i:l t 0 s c c n i . This
yields a residence tinlc of 36 s for the deposit)tin charnber
volume of (.).33 m ~ and a total gas pre.s.,,ure or 2 Pa. TIle
deposition parameter.,, tire surnmarised in Table I.
The substrate material consists of p-type single-crystal
silicun. To achieve better and reproducible film adhesion.
the subs;rates were subjected to thor;inch and identical
prctrcatmcnt. The sarnpics wcrc cleaned in an ultrasonic
bath with acetone, i.soprt)pan()l arid distilled water. Prior t()
deposition the samples were heated in vacuum in the
deposit)ten reactor f(+r !2 h at 520 K. this being folhJwed
Table i
a-B I , ( ' . : | | film dopes))ion pltr;.illl¢l¢l-S
Paralll~.'|¢r Villtlc
R F I rcqucncy 13.56 M i t e
Prectlr,,t~r ua4e,, B:I|<, ( I ( ) ' ; ) in It ,. ('1t.~
Total gas l'h)~,t.
Rcsidt'nu'c t ililu" 3fl ,
"l't+l;ll g;t., prcsstlr¢ 2 Pa
R[: p~v, cr den,,it~ ll.f+15 '~r Clli
!)(' ,,cl[-hiu,, 235 V
Stll'~',tral¢ t~.'lllI'Jt.'l'ill tire 33<+ K
t;ilm Ih+cknc',~ 125- 1511 nm
A. Ainu'. <'l al. /77mt Solid I"ilmx 312 q 199,'¢t 147 155
by etching of the .%ui'l';tce in a hydv'(+gen plasma (Usi ~ = 300
V. p = 4 Pa, H+ rlt+w l'--- 4() scorn) for 30 rain.
)'lie optical film thickness was ineasured in situ hy
means of a H e - N e laser inlerferometer. After dopes)tirol
the flirt1 thickness d, was determinetl ex silu with a Tenter
Alplla Step 2()0 i'~rol'ihmleler. The refractive iildex n was
calculated tlcCt)l'ding it) n +-Atf,.N,." m / 2 d , , with ,, being
tile ilunlher of intcrl'ere|lce cycles tilld AII<.N<.= 63"'.8 nrti.
The I'ilnl ct)nlposition and Lit(Hi! densities w,'rc mea-
sured by ion-bean) analysis. The hydrogert content was
determined by 2.6 MeV He + elastic recoil detect)tin (ERI))
[30,31], the boron content by 2.6 MeV i lB(p.te)SBe
ntlclear reaction ;inalysis ( NR A) [32] al'Ld the carhon coil-
tent by 1.5 MeV H' proton-ellhanced cross-section scat-
tering (PES) [33,34]. in view of doubls about published
NRA cress sec,i,ms [32], film composition analysis was
compared with 30 MeV ~SCI heavy-ion elastic-recoil detec-
tiorl (HIERD) [35} at Foi'sclllmgszentrum l,?,osSelldorf
(FZR). Furlhernlore, a Perkin Elmer PHi5600 ESCA sys-
tem was used to ine;.lStll'e the C / P , ratio by X-ray photo-
electron spectrosc'opy (XPS). As It resutt of these conlpar-
isons, the published cross section [32] for NRA was cor-
rected by a factor of 1.4 from 4.37 to 6.1 mb sr ~ as
described in Ref. [21,36].
FTIR tr;msmission spectra were taken with a Perkin
Elmer 1700x spectrometer in the waventlniber l'tlnge of
400 to 4000 cm i For the illtel'pretatioll and tlUalltifica-
lion of the FTIR data a ileW fol'rnalisln [29] was used, it
allows the extinction coel'ricient K of the thin-filnl samples
to be calcuhited from the nleasurcd IR speclra. It includes
multiple coherent reflections of tile IR bearn in ihe filrn
itself, multiple incoherent rellectkms in the substrate and
takes into account the Kramers-Kronig relation between
the real ;ind imaginary parts of the refractive index , annd
K.
l)ifferenl absorption bands were quantified hy !'tiling
the extirlctitm coefricicnts with Gauss)an curves aild inte-
grating Ille curves over the waver;tin:her range or interest.
The resulls are dent)ted as "inlegral extinction,' /:,, t,
3. Experimental results
Amorphous hydrogenated horon earlfide (a-B t , ( ' , : H )
thin films were prepared, with .v being varied between ()
anti t. Tile depusition paranleters were selected to yield
chemically and mecllanically stable a-B:H and a-C:H films,
in at.cordance with the results of earlier studies on tile
stability and structure of these materials [I 2,21,22,37].
Fig. I shows boron, carbon and hydrogen atom dens)-
lies as ;t fuilcliort of the relative CH.+ flow. Furtlleriuore,
tile mass density p of the I'ilms is illustrated, Widl increas-
ing relative C'tt, flow I~. file bonm atom density [B]
'
decreases almost lillearly, starting I'l'orn 9.4. I() :-~ Clll
for pure a-B:H films. The hydl't)gen ctlntelll ;HI reiliains
COllSt;.lltl, indel~entteillly of the heron and c~lt'bon ¢ o l i l e l l t S
tel' the films, at a value of al~otll 3.3. I() -~-~ cm ~ The
 A. A , , , ' , +'t ,d. / "rhi~i S~,li+l I.'ilm.~ 312 f ItJg,~.~ 147-155 14~)

r" , 3,0
1.8 E I i l l r .... I "
'[~.* ' L"_[._ 'ma;"s density ']. ' " ,
r'j)
1,7"-" i ....... ",,
F .......... .... .... • 2.8
1.6 ~ "E6.
m, " + ............"+.... +-F ...... E e...-
E X
'ik ÷ 1,5 ~ffl
E
..,..., 2.6~
E 8 1 ~ 5 El-. i .=_
o %
m ~ ,
0 ¢- 2,4
v
i • "i
_=,,6
£4- L i
2.2
-,,, • "E1-,[3.13~..1:
E
o+9. 4
3 i + , , • , . , , 2.0
- z O.0 0.2 0,4 0.6 08 1,0
C content x
,ll I
# t:i. 2. (lrtt~.xlll i':llc 17 :liltl r¢llac'iive intk'\ I! i,ir the k~iUll¢ sO| tlf saillr~ll.,s
ill • boron i FiT. I ,i~ ii ltllll..li~lil o1 lhc, t-:ll'llOll c'Olllc, lll .I, I.inc'~ iil'c' OII1', :1 7uitl¢
it,, ill
.... i carbon
II s. hi Ihe e'~e.
A hydrogen
V= 1 ~ I • I
n
0 20 40 60 8'0 100 Fi#. 3 ilhL,,trales FTIR ti'ailsmi:,sitm spectra of films
CH 4 flow t total flow ( % ) with dift'crcnl .t' over Ihc whole x~[Ixentirrlhel + I"ari~.¢ liiea-
I;ig. I. I)¢l~elld¢llU'e o1' h~i'tm. ¢lll'l~oll and I1):cll't~gc'li ;lltilll ttCltsilies sured, froill 4()0() to 400 cnl I Tlie ;li'IsotTIlioil bands o f
Ilu'll-htind ~idc)Oll lhc' iu'hilixc ('11+ Ihltv (('1f~ I h l t v / l ~ l a l II,~vi. The Ill0 a-B~ ,C,:Fi I'itm.,, arc altributed to the I'ollov¢iri~ vibra-
lol:il ~is I'lox% alid lll¢S,,lllt ' ;ll'¢ kCl+l c'~lilsl:ilil at II) nt'cni Ulld 2 I~cl. tional ilit)l.lcs.
reHx'ciivel)'. The Ili;L~, d e l h i ) /~ is sllllXXll t~n the liTlil-li;illtl s¢:llt'..,% Tile l';.lll#O betx~.e0rl 2"7()() and 3 I()0 ¢111 i nlloxvs I'n'oad
l)'l+ical t*lltlr h;ir is shllxvn for lillt, dillil ptliill or cacti c'llr~c,. I.iile~ ill'c, olil)
ahnoi'plitm haml.s, x,,iliu'h ul'e t.turihuled to dil'l'ereilt C - H
a ~uidu' Io the c,)e.
vil'liational band.', [.19]. For pure a-B:H tIle strelchiri~. ~.il'lra-
lit)It of tile B - H terrriinal bond aPpcals at 2,'i6 t) cm I
[ 15,1"7. ! R]. This hand decreasen in inlen.nily for fillrls ,,vilh
ctirhoil Cillltcni [('] illerease.~ iiiont)foni¢;illy. I)LII llOl Iin-
higher carboll COlllt~lll ilrld nhil'ts !~ louver xviix'enulllhcrn. ~in
e[il'ly, with I~, up !o ii X'~llil¢ tlr ahiitlt FI..:I:+-.I() 27 Ctll i
d¢,~crihcd furth'.'r I~ehlw (,see Fi~s. 5 and 7), Tile vcr),
The combh]¢d boron allti Calhon atom density anti. ,sit]eL'
hl'Oad balltl, cxicntlili&t ox'¢r a IanTe or liiOl-e Ih~ill 700
the hydl'ogon cilnlenl in ii]del~endonl of I~,. at.,,o the iolal
cnl i with ili¢ peak ina.%ilnunl al aboul 21t(ll)¢11l 1 is
atom den,~ilv o f l i l t t'ilm.~ tlccl'O;l,~e,,, rr/ini pure a-17l:FI to
allrif~lilotl I',i h)'th'ogon in ti Ihr~2o-c¢nll't? i~olitl I~olxvecn two
pure a-(?:H with a lnillilllUm tlensil)' I'or I~, = t).t~. From
Illc,~ data Ihe in;t,~,~ tleii,~ily p l,~ C'tllc'uiltllod and I~)Ulid Io h0
~il~otli 1.72 ~ c'm ~ t'lir holh pure a-B:l-! and a-(-':H rihns,
iglms with .v_< 0.26 [ll-C o1 .shllihu. all other ICrlitlr), ii-
I~ i ,(,,:FI film,,, o1' lower sl}ecil'ic delisil)'. A nliniinuni
liltiSS t l e l l S i l V ( I j ~. 1.41,I ,, t i n ~ ) is til}sclX't~d tt)l x = (I.71
In the followin[z, the I'iln] prop(rlics arc discussu'd ~i.,, a
I'unclion t)l" Ihe u'~ii't~t)n COl]loill .v or the I'ilins. xvllich is
dei'ined us lci/(lcl + iitl). '~-i x = 0 '6

In t"ig, 2 Ihe dcpo,~ilit)il rlilO Ix' ~itltl relrac'iive index ~1

;,11"0 p l o t t e d X'121',~Ll.~ t h e Cal't~oil COlllk?lll .x. f o r the deposilioi~
l'alo R there is not [i ,~hnpIo linear rclalion. V~ilues or pure
a-B:H (6.5 nnl inin i) anti a-(':l-! (4 Ilin iliin l) are
I),l]it.'al i'alcs I'or I'ilnls I~rel)ai'ed illitler Ihcse dcposiiioit
ctlildilitm,~ 12i,.~l. I:roiil .v = I) to al~olit I).15, Ix' in ~iPt}l+O'~-
imaiely Ctill,~lanl ~il [il'litltltl 6..~ tlln mill ~, t:l+Om ().2~ tip IO 4oo0 3000 2000 ~000
.x= {),6, R is rt}ughly CttliSiaiil al at~lltlt 5,7 nnl milt i l'or wavenumber (cm ')
,x > (),~, R decrea,~es to the hlwcr tlepo,~ilit)n rates I),pical
t'i#. ,t I.'I'IR li;illsllli,~lOII ~pCCIl~l el ,t-Ill t ' < . l l lilnl, x~iIll ~11%i11,~
or a-(',,I-I i'ilnis. The reri'acliX'e index . (I;i7, 2) Llecrea,se,~
~.'i.ll't'l*ill I,.'Ollti.'lll %- The ,Irucilll," ,it ;tbotll 2.~.':,() ~.'lll ' i'., ~.tll illMl'ulrlli_'lllt~.il
ntlinolonicall), willl Ih¢ c;ii'l~oll ¢onienl l'l'tlnl ~1 --= 2,$4 lit- ~lllcl'~t~.'L tl'll~.' IO ~.'l!<~ltt~¢~. ill IIIl.k' I'~.",.il.tLtL|l ('(), a11t.~tt|tll t~l" Ih¢ Iti+2;ll'..l.ltiil~
it:It) I(l 2,()14 (a-(':H), Valile,~ i}l' l'ilnts with ,v > 71)';~ arc' Ch~mll'li.'r. I:t}l ~.l,ltlt b ttlC bitnl.'lill¢ o1 e,lth ,,r, et:lrmll i,, ,ll'Irtt-t'ii'llriat¢t ~
ilearlv the Sllllle tin the,so o1' pui¢ a-(':ll. qlilted.
15(I A, A m . ' . u / a l , / 7 7 f i , Solid/"ih..~' 312 f lqq,~J 147--155

I~ol'on ;itoins ( B - H - I - ' ] ) [1 I, 15,17. It)I. li rapidly decreases

in intensity with increasing .v and is visible in P'i~. 3 only
l'~lr .v = (i aild very weakly for .v = 0.26. At .t+= 0.5 ii tlll.~
colnplt?tcly Vallishcd. These two hydrogen relaled hands
'
O

"----"
is
4'" o,,,..,," "-,-""
x 0.86
f
tl
,
x'
, <,,i~
~+~
,4,
' ' ' ' '1
ill't2 discussed in detail for ptil'12 II-B:H l'iln]n in Ref. II71. ..~ ./ ~ ~ •
h ) r fihn.~ w h h hight~r tral'bori conli:nl V~il'iOtl,~ very small x = 1 / /
10 , '
pcak.~ aprl¢~lr betwecn 12IX) and 16(10 t i n i rc.~iilting I'lonl
dift'erelll f - ~ t and f - f Vibl'ation.~ (4()]. The niosl r)l'onli - O ,i,, ,' ', '{,
.,,', O. 3
liClli l'eaturc of B / O conlr)o~ill2 film.~ is die 13 -C stretch
band :!! ahotil 1200 t.'in i [18.41,42]. Accordhlg Io Shirai
i#,,~ . . -.,, .,% ~.
el at. Nil. this b~,lnd i.% all exli'iitsi¢ B - C vibration nlodo , i

dtll2 to ci.il'bOll bolldl3d in the I'orn] ill" iorn~inal - C H ~ ~ '" '""~'"'.., ~'-%"x,~
glOtlll.~, which nlean.~ lhal c:lrhon hondt~d in ihis way is nol
i.1 network li)rnier. Ternary :t-B i , C , : l t alloys also show 0 . . . . i ,
2800
, , , ~ . . . .
2900
'h
3000
"?". "."',
an absorption band at about 1500 cm i This hand is
wavenumber (cm")
attributed to an intrin.,,ic B - C vibration in fi~rm o f - C - B -
B - or - C - B - C - chains [41]. hi contrast to Ihc cxtrinsic FiI:. 4. i!xlillClion coetficicnt ." of the ('--II nlrclchill~ vibr:~lhtlis ~1
,(" :11 t i l l n s ~,~iih var)iilg carbon ttllllc'lil 1,
;.l-ll~i
nlode at 1200 cnl i carbon bonded this way is a con-
~litLiCni o f ihc n¢lwork, a so called network fornler. LIp io
I'i'¢tltlellt.'it~.,, of abOtll t1()0 cm i B - B nctwol'k vibration.,, arourld 2000 crri t for Iih'ris willl c;irhori ¢(lritcrit .v of up
fornl ~1 i,'oillinilOLl.~ ab.~Ol'l)liiin bi.llld which i.,, weakly visible to 0.71. This region is correlated ~ iih vilmllions of hydro-
in Fig. 3 with a small peak at ahoul 8()() cm i [41,43,441. gcn bonded to sp~-hybridizcd carbon [39.4()]. The extinc-
li should be nlcntioilcd lhat wc do nol find any vihralional tion in the wavcnumbcr range of 3()0() cm ~ and hi~her.
hands ill the wavi2ntlniher ratine above 3100 cm ~, Ihc wl'icrc vibrations of hydrogen hondcd to .,,p-'-hyhridizcd
rlingc whore ( ) - H vihratiOll ballds (ahoui 35(1()/325(i t i n carborl urc observed [3q,40], is very small. Furthermom'c.
[20]) should appoar if lal'gt2 alllOilillS of ~lxygt211 WCl'C the integral extinction /'lilt over the whole wavciluilil~cr
hicol'r)(iralt?d in the filn~. This shows ihat these I'ilms iire range from 2700 Io 3100 cm ~ increases monotonically
c h e m i c a l l y siable, Qualitaliv¢ly simihir infrared .H~¢cli'a of with carbon coritcrii up to .v= ().71. For concentratioris .v
ii-B:O:H t'ili11.~ wcrc rttpl)rlcd hy Dckclllpciiccr ¢t :il. l_ 3] him'gcr ihari (1.71. especially for i'~um'ca-C:H, a shift of K,~,,
alld W~l~ll¢l" ¢1 al. I24]. w h o also nl¢~i.~tll'cd Ralll;.in ~pt2t.'lrli to larger wavenunH~ems m~d a comparably tar<ge extinction
;ind the Irihological pi'operiies of tlicsc fihns. in Itl0 wavtmuinber l'all~0 ~ 300() on1 t is observed. Elu t
Some further absorplion bands duc to impurilie.,, from dt2¢l't2~.l.%t2,% n]oi]olonical I)'.
the suhstl'atc inlerl]lce or fron~ measurement aiicfacts can The cxlin¢lion cocffi¢ieni K of the B - H absol'plion
be observed iri Fig. 3: At abotll 235(I cm i the asynirrtclric t~and (Pig. 5) dccrcasc.~ nloillilonk.'ally with int:rea.~intg
vibration,,-: of C = O [45] appear as an artefact of t!i¢ inca- Calhon t'Olllt2nl .t, The peak nlaXiltltltn K ...... shift,', I'rolli
surcmcnt, cau.,,cd by a variation of the C O , coillcnt in the 256tJ cnl t for t'ilnl.~ with .t'_-[ ().15 dowil Io [thllul 2495
:lmbicrll atmosphere while ll'ic sarril'ilc arid background arc cm t for . t = 0.71. iClllahiil%~,,, ¢on.~!alll for hiuhcr t'al'l~on
bciri,g measured. A .,,rnldlcr vibraliori ut about 2100 cm i
is supcrposcd on ti'ic B - H - | - I band Tiii,, can bc utlributcd 0.06 i . . . . F ~'~'~,' ,
Y"k.
,
"
1 , , , , i

to hydro,~cri bondcd to silicon [46.47] at the interface

between lhc suhstratc and film due to h vdrogcrt irriplanta- 0.05 x=O=O/~
lion by hydrogen plasma etching of the suhstratc prior to x -: 0 1 5
dcposilion [2(I]. ERD nicanurcrncnt.,, of Si .,,uh:.,tratcs after a "- 0,04
~,tandard cleaning procedure sho~,%~ h vdrogcrl al'cal d¢linitic.,,
of about 2. I() i<' cm -'. corrcnponding to about 20 hivern
O 0.03 x 36
of l'lydroBcnatcd silicon. A very .,,harp band is tourid at
11()4 crrl I and is assigned to antinvnu]]¢tric vil~ialiolls ~ll (3.
Si()~ [4t~,4tJ]. "~ 0.02

As d¢.~crihcd in ,~cclion ] the CXlinctioil :',,~cificici~i k" "

wak calctilated frtinl lhc t 7 1 R irall.~nli~cion nl~,.cfra. Fi{zs. 4 0.01

and 5 ,,,how SOlll~ o1 lh¢ rcntilln of !hcnc c';.llctllat;Olin for the

vcav¢iltllllhcr i'ogilln.~ fl'oill 2720 io 3 Ill()Clll i ;.ilitl 23:J()t~i o,oo -

2710 cln i. which corro.~pond Io the r¢,.<,~i~in.~i)f' ( ' - H ~illtl 2400 2500 2600 2700

13-H ~il~l';tlional balidn, rcnpoctivelb'. wavenumber (cm ')

The cxlinclion coct'ficicnis ~ of Ih¢ ( ' - t t ~ii~i'~ilillnal t"lg. 5, I'\lillcli~ql c~elliu'ient ~" of Ihc 1| II Ml¢l~.'hillU I'WHiLI O1 d-
blintl.,, .,,houri1 ill lgl:. 4 exhibit nlaxhllilln valilcn t<...... al I1~ .1",:tl fill11., v. ilh '.ar.~illg citl'l'~oil ,t.',lllll£'lll ~.
 A, Amu'n ~'t u l , / 7 7 1 i . ,%did I.'ilm.~ J I 2 f 199,~t 147---155 151

' i I ' I '",' • ,, 2580

0 ' ' ' ' I I ''' I

2560
15,
2540
.. o., B-H-B 1 i
E
v --I-- B-H 1 -"" 2520
E
LU .9.
° 2500 0
t- 10, • OIO
O
2~80
E
1220 B- • I
1200
8' I c) i i I I
1180
".,,. "!..i
I
ol I I
: :oo
.... ....I ~ I ' I i
1t60
I
1140
0,O 0.2 0.4
C content x
0.6 0.8 1,0
U0 o'2 o'4 o'6 1.0
C content x
Fi#, 6. lnlc~ral exlinciinn I'+'i,,~ of lhc I'1-1-1 terlnin;il nnd i 1 - t 1 - I ! hrid~c FiT. X. Peak shill of lt~c lerniilltll Ii-t.I alid Ihc CXtt'itlsic' B - C sll'clcllilll
I'li)ltd It,<, ;.i l'llilc'lillll ill" lhl-" L'ill't'li)ll c'llllll.'lll I. vil~r;lliOli~ an ~l fliilclilul ~I" Ihc c':lrhlqi t.'OlliCtll ~.

content (Fi~. ~), F:urihemmre, the full widlh half nlaxinlunl

F W f l M increase,~ nlonolonicaily from 03 cm i for pure 0.35) and then decreases, E~,,, increases ,~imilarly up to a
a-B:H films tip lo 131 Clll 1 [11 .x" = ().3('1 ~.Llid l h e n d e - broad maximum of 7 6 - ~ l cm ~ between .v= 0,48 and
Cl'eiisCx I() abol.ll 110 on1 i t'~w oath(m-rich films. 0.71, as shown in Fig. 7. The maxinlum of this B - C
The different boron-hydro[.zen and boron-curb{m ub- xlrelch b:md. ~.',,,,,. shifts monohmically will1 increasin,,.~ .v
,~orplion band.s were quanlil'icd by calculalin,g lhe inlcgral I'mnl 115()crn I al . v = O . l ( ) I o 1230 c111 I al .v=O.B6
extinction Eh, , i.is de.~crihed in Sccli(iri 2. The re.suits arc ( Fig. ~).
presented in Figs, 6 and 7. /:.'h,, of the B - H slrctch bond l-t, . of the B - C vibrational band at about 15(X) cm .t
( t : ; h , ( B - H ) ) arid IIie B - H - B brid,#e bond ( I - I , . ( B - t t - B ) ) iilcrca~cs xvilll .v tip L(~ a IHa×irnum of ahoul B c111-i al
deci'ea.~e monotonically with increusin~ .v (Fi#. 6). While 0.71. In u'onlla.,,,l !o die 12{)0 ¢111 t B - ( " t,;Irelch bond. only
/-I.,(B--H) decreases almost tillcarly wilh x and is dc- a IriflinE {.leer'ease of l:'u, , was l'oulld here for lhe filnls
leCll.lhle even for the B / C lel'ni.iry all~.ly with the snlnllesl WiIJ~ IOV'eSI b ( l l ' ( i n ¢0II10111.~ (.T = ( ) , l ' l ( ' l yields Elm ~ 7
boron content itlve~li[z:lied ( x = ().X6). E u , , ( H - H - B ) cm ~). "lhe nlaxinlum ~if this band. ~:,:,,,. sliBhdy shifts
rapidly decreases and is hardly perceplihle for .i.'> 0.26. with incruasi11,~ .~ l'mm about I~05 cnl i al x = O . l to
Tile bl.uld wilh Ihe lartzest extinction c,,icMcienl , i,~ Ihc I~15 cnl ' al .v= 0.71. Only fnr 111¢ films with file lowest
B - C stretch bond i.iI ;ihout 1200 on1 i. n" iilci'easos 1110110- b ( ) r O l l CLIIII¢IIIx \VI.I,~ ;.I slronBer shifl of ~,..,. up Io 154~
tonically wllh lhe cnrhon Coilleltl tip Io .v= (),414 (~,..,, = on1 ~ (~hserved.

• T ' I

80 ', i--i .,= 'i 4. l ) i s c u , ~ i o n

i ',
4. I. l"ilm pnqn'rlie.v
.-. 6O ~# # ,~
E I
o
, i ('omp~.~sitilmal anal v.,,,in nllov,'ed that the atom density of
40
Iii boron decreuse,, linearly. 1hal of hydrogen remains con-
,i
o nlallt and thai of carbon increases sli.2..hlly mmlinearlx' with
o 2o
.~_ rI
I l-=- B.o,,2ooc hlcl'eanhl,,,e ('H.~ partial .'.-z'nstim,,. TIle mass density, of the
II a-It:H and ;.i-(':H fillll.~ are nimilar, p = 1.72 ....,', cm a
--
~
0
8
I
1 value lyl'fical of h:n'd amJ denne m B : t l [17.20] amt a-C:ti
I I "..1. ,0"
I O' ° o I' . ,I 1 I50] Iilrn.,,. !11 ¢onll'~ari.,,ml, nolt, polymer-like n - c : H films
e-.- have dcllsilie.', of I ~ ,, cm ~ mId len.,, and dinrnorzd-like
O 0 , -_~ 0 '0 " , I'i1111,,, of typically, ah.m _,_" "~ ..- cm " [50.51]. Ternary
2
0 [ -' O- - , B - C { 1...........
500cm~) n-B I , C , : | ! film,~ were I'~,.md to I'~c Icsn dense, ,.vilh a
I ' ! . I I I t

O.0 0.2 0.4 0.6 0,8 1.0 tlislirL¢l mininlunl al .v = ().71 ( p ~ l a x ~- cnl ~). A! Ibis
C content x ¢OllCelltrl.ltiOli A= 0 . 7 1 o t l l l 2 r fihn properlien alnn ,shox~
I:i#, 7. hllegral e\lhtcli~m I..u, , ~ll the.' l l - ( " slfL'h.'hin# ,,ihrali,ms ,kl 121111 I'~.;ll|~lrk~.|l'ih? chall~u',', stlu'h u'., cxifoilla Or chall~'s hl slope.
cm t ~lnd 15(11)cm t The refractive index n decr,.,ases linemix Io .'u--().71 and
152 A, ttmu'n el ul. / 77dn Solid/.'i/ms .112 f 19t)lCJ 147-155
renlairls constant for higher carbon contents (Fig. 2), The
extinction coefficients K of tl'ie C - H (Fig. 4) and B-C
(Fig. 7) vibrations at 30(X) cm ~ and 1500 cm ~, respec,
tively, tire maximal for this carbon content. The peak
I
integral Etn t of the B - C stretch bc,nd tit 1200 crri
significantly decreases above .,r =0.71 (Fig. 7) and the
gradients of the peak shift of the maxima of the B-H
terminal and the 1200 c m ~ B - C stretch bonds distinctly
change (Fig. 8). Furtl'icrli~ore. iri another study [4t)] it could
be shown that the emsioll of a-B I ,C,:H films in liydro-
gen and hcliuln plaslnas also undergoes i.lpl'lreci;ible
cil:lnges for x = 0.7 I.
4,2. Film .~trtu'ture--ident~/h'~ttion and qmmt(lh'ation n f
t ihrational hatul.v
FTIR analysis using a new fcwmalisrll [29] allowed
determination of the extinct;or; coefficient and systematic
quantification of tile different absorption bands. To tlic
best of our knowledge, this is the first time that the 1500
crn l B-C, the B-H and the B - H - B barlds have been
observed and quaritified over the whole range of a-
B I ,C,:H fihris from pure a-B:H to a-C:H. The 15(10
cm i B-C barid has only beer; rricritioned for a-B i ,C,:H
films in Ihe basic work of Blurri et al. [18]. who could riot
describe it further, since the carbon content of till films
rneasured was lens than 14"A. The most prominent B-C
absorption band was the object of investigations of Shirai
et al. [41] for a carbon content .v < 0.5. in Section 4.3. the
different absorption bands ;ire discussed with respect to
c~mposition and slrticlure.
4.3. Hydrogen I~omling.~'
hi pure a-B:H films I'iydrogen is bonded Jr; two different
cnvirorimerits which are ca:,ily distinguished by their
.,.;tretching vibrations. These stretching vibration,,; appear at
2569 cm = for the B-H and at about 2000 cm = for the
B - H - B bridge bond (Fig. 3). Pure a-C:H films show
various, wcil-l:nown C-I-! stretching vibration,; at 2800-
3100 cm ~. The inlluence of composition on these vibra-
tions is different. K......(B-H) shifts down by about 75
crn ~ with increasirig carbon content (Fig. 5), whereas the
position ot' the C - H band seems to be unaffected (Fig. 4).
The B - H - B bond already vanishes for small carbon con-
tent.'., (Fig. 6) and no shift cotlld he ob,~erved. Shir'li arid
Gorida [52] did not find a systematic tendency iri the shift
of the C - H fretluericy and. in contrast in nur observations,
of the B-H frequency with the C fraction which they
investigated in the range or 0 <.t, < 0.35. There rriay be
two reasons Ibr thin. First. Sl'iinii and Gimda [52] state',l
th;it tlleir metl~od o1' deterrniriing the carborl content is
subject to a rather high degree of uncertainty, and second.
the peak shift of the B-H barld heconles sigrtificz'nt only
for carbon fractions above 0.26 (see Fig. 8). if il is
assurned that Shirai el al. overestimated the cai'b~m content
oi' their films, then lllese observations ;ire not necessarily
contradictory,
The difference between constant absorption tYequencies
of the C - H bands and l'requetlcy shifts of tile B-H band
might indicate the different ways in which hydrogen-carry-
ing boron and carbori atorris are bnnded irl the a-B 1 ,C,:H
network, If the vibration is an intrinsic mode [52], the
vibratiorial frequency is likely to clw,nge with compositiorl.
The extrinsic vibratiorl ori the other hand, is less irilluenced
by structural and corrtpositiorial changes of the network.
The frcquericy shift of the B-H barid might, iherefore,
indicate tl'lat boron is bonded ;is part of the network as a
,.,i-called network former [52], whereas the constant ab-
sorption frequerlcy of the C - H bands points to hlrger
arnourits of terrninally bonded C-H groups.
Sal.~ et al. [I 7] studied the llondirig of Iiydrogen to borer;
in pure a-B:lt t'ihiis as a I'unctinri of deposition par:lmeters
by infrared spectroscopy and estimated the absorption
cnnstants of the different vil'watiori,'lt bands. It was derrlon-
striated tlmt for stable films, such tis the a-B:H I'ihris in this
work. about 30q of the "~ydrogeri is im:orporated in the
II'lree-centre B-t-I-B br,dge bond and the rerriainirig 70%
in tlle B-H terrriirlal borid. Although it cannot be ruled out
that different matrix environments due to increasing car-
hem content alter the absorption strengths, we use in the
following tile irllegrated extiriction I:'n.e to discuss changes
of the amount of hydrogen bonded to carbon and boron,
From a comparisor~ of Et,. it is obvious that ever; small
amounts of carbon incorporated into the arnorphous boron
network will destroy tlii,~ B - H - B bond (Fig. 6), Arialo-
gt~us observations were rnade for unintentional incorpora-
tion of carbon arid oxygen into el'tern;tally unstable a-B:H
films deposited at low substrate leirtperalures and ion
crlergics [21], whicli also leads to a disappe:u'arice of this
band in the IR spectra, l'+u,. of the B-H terrriinal bnnd
E;,,t(B-H) orl the other liand decreases almost lirlearly with
the boron content. Assurriing that the ahsorpliori strength
of B-H does riot charige too niuch, we COllclude that the
ainount of I'iydmgen borlded to boron irt this terrnirial bond
decreases proportiorially to the boron content. Considering
that tlie hydrogeri coriterlt [H] is constant at about 3.3. i0 "~2
cm ~' over the whole range of concerltrations, a rapidly
increasing arnount of hydrogen must be bonded to carbon.
Urif~wtunately, hydmgeri bonded to carbori is very diffi-
cuh t(~ quantify [14.37]. Here one ti,'is to consider tl'ie
different hybrid;sat;otis of llic carbon atorrls (sp ~ arid sp~),
the t turnber of llydroger~ atonlS bolldcd to one carbori atom
and the symmetry of the specific vibration. The absorption
band between 280/)-3100 crri = coral'}rises riille different
C - t t vibrations [39] with differcrlt absorptitm strerigths
and their c~mtribution to the tolal absent'piton change with
the actual network structure [37]. Nevertheless. from the
shape of the C - H extincti~m (Fig. 4) it is possible to
coricludc qualitatively the liybridisatiori of carbon since
most sp "~ C - H vibrations appear ahiwe 3OO() tin l,
whereas .',;p~ (7-H vJbl';ilJons appear below 3(il)tl tin t
 A, Anm'~ ul td, /77ff, Snlid l"ilm.~ .¢12 f 19~A'~ 147-- 13S
The pUl'¢ a-C:tl filnl (.v = I) shows a significant fraction
of sp ?, as is expected for hard a-C:H films (sp-'/sp ~ = 3 - 4 )
[14,37]. A small l'raetion of boron ix ah'¢ady suMcient to
cllange the structure signil'icantly and only small or no
absorption is detected ill wiwentlllll)el'.~ > 3000 ~.'III i for
lernal'y a-B~ ,C,;I-i filnls. Cm'bon in Ihe ternary boron-
carbon alhly is incorp~rated predominanlly in the sp ~
hybridisation slate, These chan~.es from carbon sp-" to sp'
hybridisalion are itnportant especially in the discussion of
the erosion of the a-B~ ,C,:H films by hydrogen [28]
since sp ~ hybridised eat'ben seems to he a Iweeursor 1"{>1"
chelnieal erosion oI" carbon [26,27],
The changes from sp: to sp' hybridised carbon explains
ftu'tl'terrnoi'e, why the filins also incorporate relatively COII-
Slilllt hydrogen iltOlll densities at lowest tarbell ~.'Ollleill, ill
spi~.e of the stl'on~., decrease of the B - H - B bond. Since
sp Lhybridised carbon is able to bond up to three hydrogen
illOlllS, the toss of hydrogen bonded It~ borolt in a lhree-
eelllr¢ hond can be ¢olllpetlsaled if in lilese Iow-carhon-
contenl i'ihlls lhe relative anlounl of hydro[zen honded Io
carbon ix ahoul 0.8-I,I) (¢ompai'ed wilh H / C ~ 0.4 in a
hard a-C;ll film), which ix lypical of soft, spLdominated
C:H liln'm [14,37],
4,4, B n m l i , , ~ n . f l ~ n n , , I , ( ' u r h n ,
As nlelltioned in Section 2, tile most i'~ronlinenl feature
of the F H R spectra belongs to an extrinsic or local B - C
vibrational mode, with C not considered to he a I~etwork
eor~stiluent [41]. i]iuln el a]. [18] foulid this band at about
100()-1200 em ~ Ibr small fractions of carbon in a-B:H
and eslimaled Ihe carbon c'ontent from Ihe ahsol'plion of
this hand hy the Beer-l,anlhert law. ,"ihirai el al. [41] found
this hand to shift from 1050 cm ~ to 1200 cm I with
illCl'e~,ISil1~ {.'arholl u'OIItellt, silnilarly tt) our ille;.ist11'elllelltS.
The lack of knowledge on the ;Ibsorptitm strength of thin
B - C vibrational mode prevents quanlilatively deduct|eli of
the carbon conlent bonded exti'insically as terminal l~ontl.
lnleresling structural inI'orlnation would he provided hy
quanlil'ying cai'hon bonded exlrinsically in a terminal bond
and carbon bonded intrinsically as a network atom ¢Ollll~a-
rable to carbon in the I~lzC~ crystal [53]. Nevertheless. il
is possible to conclude qualilativclv th~II carbon honded
extrinsically to heron network atonls tracteases almost lin-
early with x up to a hl/oL|d nlaximtml at ttbOtll .v = ().45-
0.75 (Fig. ?). This inaximtlm correlates wilt~ the minimum
mass density, which ix re:~sonai~le since larger quantities of
extrinsic bonds imply a less cross-linked Mruetlll'e.
The second B-(" hond nleastwed is tl~e ~ibration at
about 1500 em '. ()l'~sei'ved for the t'irsl lime ILv Blum et
al. I I S]. lhi,; ahsorptioll hand has mostly been i,gnored since
il is relatively small at tlle high-ener#y side of tlle edger
B - C vibration. This vihIalion is pI'eSulned to he an inlriil-
sk." vil'~i'ational mode like those oI' tile eenli'ed C-I:I--(" or
C-B-B chains delected in ,:i'ystalline l~oI'On carbide.
Kuhlmann el al. I531 showed these latliee mr)des to Ix'
153
located between 1530 and 16(X) ern ~, in agreement with
our observalions, Ihe stretching nlod¢ of the C - B - B chain
[.531 shifts toward higher wavenumhers wilh incl'easin[z
c;.II'boll¢Olllell|, |=or B I2Cr~,. which repl'eSelltSthe carI~on-
rich limit composition of boron Carbide, both Illodes ;ire
i'otnld at about 1580 tin I [53]. Since the BI2C'~ crystal ix
the hardest solid ~,illlt,lll'g VIII'I(ltlS boron nmdilications, lilts
vihration ix expected It) o c c u r in B I 2 c t It| ;1 higher
wavenumber lhan in a-B I ,C,:I-i (1505-15-15 cm I).
Finally. We altenlpt a firsl estinlalion of the absorplion
¢OllSt;.tlll of tile eXll"hlsit." B - C vibrational mode at ii~'lOkll
1200 ¢lll I { All(" ). u,~ing the [:TIR and IBA data of films
wilh 0.26 < x_< 0.71, AssunfiI',d. thai llle absorption t.'otv
slanls for the B - H and the B - H - B vibnltioiial modes
(Aim and A,,.~) delermined for pure a-B:H [17] are also
valid for ~.I-B I ,C,:H I'ilms. we arc able Io calculate tile
density o1" hydrogen bonded to boron [I-l(t,t]:
[ti(B)] = A,,,,- I:'I,,,(B-H) + AI,I,,,./:',,.(B-H-B). (i)
with EI.,(B-tl) and EI,,,(B-II-B) taken from Fig. 6 and
A , , = (3.04 + 0,47}. I(} 21 till 2, AI{III { = (0.4~ +_ O,076)
i0 -'I ¢111 -" [I 7].
Furdlerunore, with [H(B)], the density of hyd1"o~cn
bonded to carbon IH(C')] is ~i\en hy
[I|(C)] = [H]- [H(B)]. (2)
with llle total llyd1o~en atom dellS|Iv [H] t;,Iken from Fig. I,
Tile extrinsically bonded carbon exists in I!1¢ l't~llll o1'
lernlilml -CI-I ~ ~tOUl'm.
o. This allov,'s estimatinn of an upper
limil of the density of extrinsically bonded carbtm [(."., J, If
it ix assumed lllal all hydroser~ bonded to carhon in bonded
to exlrinsic ¢arl~ol~ (as -CI-I ~ ~roups). then [C'.~] ix one-
third of [(H(C)]. The extrinsic carbon in the form of - C H
gmUl'm is bonded either IO boron or carbon, if it is bonded
to horoll, it will COiltril'~ute Io the intensity of the 1201)
cln ~ B - C vihratiort /'h,,iB-C): if it ix bonded t,.l carbon.
it will sol, As an upper limil v,,e assume lhal all exlrinsit."
t.'iil'l'~oiI is holidcd to I~Olon I'or tile exalnilled l'iiil~e of
ctmT.~nitiow, (().26 _< ,v _< 0.71 ). Then ,4~w is ¢alcuhlted t~.~
he
to,,]
AIU .. "~ ( -- (3)
- l:'h,,(B--(') -- 3 l:'h,,(B-(')
~itll /:I,,,(I:~-C). the trite#rated extinction of !11¢ B - C
.~lreteh bond at aboUI 1200 ell1 I l~ein£ laken I'rolll l:i,~a. 7,
()n tile basis ~f the,,e ;IsMlillptiOIlS,~Ae estilll;lleth," tlpl~er
\ altlc t)l' ,~l~t. 1~) hc
Alt t. S 1.3. I() ~'n em '. (4)
"~t~ is ver v small compared ~ilh tile at~sorplJon con.
MIIIII~ "~lUl ;.llltl A I~IIII,Thi,, llleilllSthat tile correxpolldin,g
o,,¢illatorstrength i~,relatively high .,,ince ,~ i.~ i~roportional
t~.~ I1".,. inscrse m" Ihe oncillahq" ntt'¢ll~lll. Nevertheless. Ihe
i|lliOiHl| of Ci|l'llt.IIli~olldCd e\Irhl.~i~';lllvIo boroll is IiO|
 154 A, A t m e , ,'t al. / Thi, Solid I.ilms 312 11qg,~t 147-155
n e g l i g i b l e since E h , ( B - C ) for the 1200 cnl ' vibrational
b a n d is r e l a t i v e l y high (see F i g . 7). In the range oF
c o m p o s i t i o n s c o n s i d e r e d here t 0 . 2 6 < . r _ < 0.711 the con-
c e n t r a t i o n o f c a r b o n b o n d e d e x t r i n s i c a l l y to h o r u n is be-
t w e e n 18 and 2(V,~ o f all c a r b o n I.II',)I11S.
A s i m i l a r e s t i m a t i o n o f the abs~rptio:'~ c o n s t a n t o f the
intrinsic B - C vibration at ahoul 150{) ¢ln I is s o l p o s s i b l e
on the basis o f these data.
5. S u m m a r y
;I-B t , C , : H films w e r e d e p o s i t e d o v e r the entire 120111-
positional r a n g e from pure a - B : t i to pure a - C : H films, T h e
d e n s i l i e s oF the a - B : H and a - C : H films are simihu' ( p
1,72 g c m ~) arid typical o f hp.;d and d e n s e a - B : H and
a - C : t t films, w h e r e a s lel'llal'y ;I-B 1 , C , ' ! [ films tire less
dense, withaminimumat.v=O.71[pm 1.48gem ~).At
thin c o n c e n t r a t i o n .x = O.71 otb,,:r film properties also un-
dergo appreciable changes.
T h e b o n d i n g o f h y d r o g e n to the dilTcrent n e t w o r k COll-
stituents, b o r o n a n d c a r b o n , d r a s t i c a l l y elranges with vary-
ing cornposiliorl. R e l a t i v e l y small a m o u n t s o f c a r b o n al-
revdy s u p p r e s s the b o n d i n g o f h y d r o g e n in a t h r e e - c e n t r e
b o n d b e t w e e n tw~ b o r o n a t o m s . H y d r o g e n b o n d e d to
b o r o n in a t e r m i n a l b o n d d e c r e a s e s a l m o s t linearly wilh
i n c r e a s i n g c a r b o n c o n t e n t o f the films.
C a r b o n in the ternary b o r o n - c a r b o r ~ alloy is irtcorpo-
rated p r e d o m i n a n t l y in the Sl ~ hyhridisatiorl state, w h e r e a s
pure a - C : H t'ilms s l m w a s i g n i f i c a n t fraction t)l" sp-" c a r b o n .
A n o t h e r o b j e c t o f the e x a m i n a t i ~ m o f the film n e t w o r k by
Fq"IR w a s the dil'F,:renl b o n d i l l g s o f boroll to c a r b o n . T h e
1200 c m I e x t r i n s i c B - C vibrali(mal rhode a n d the 1500
c m ~ B - C i~el.vvork vibration w e r e o b s e r v e d and tlUal~li -
fled o v e r the w h o l e r a n g e o f a-B I , C , : H film c o m p o s i -
tions and the ahs~wption c o n s t a n t o f the e x t r i n s i c B - C
vibrational nlod¢ tit 12(10 Clil I WI.IS e s t i m a t e d .
Acknowledgements
Special thanks arc d u c to S. G r i g u l l from
F'orscl'lungsz,'ntrurrl R o s s c n d o r f ill I ) r e s d c n ( G e r r n a n y ) I'~w
p e r f o r m i n g HIF~RI) c o m p o s i t i o n a l a n a l y : , i s o f Stlllle Of Otll"
samples.
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