.

-7
b 0
Characterization of C-B-N Solid Solutions Deposited from a
Gaseous Phase between 900 and 10S0C
Frederic Saugnac. Francis Teyssandicr.' and Andre Marchand:
.-\quitaine. 3516'5 S:.t;m Medard-en-Jalles Cedex. France
The composition. the structure. and some physical proper
ties of boron-carbon-nitrogen solid solutions prepared by
chemical \apor deposition (CVOl have been investigated.
Both crystalline films and amorphous granular materials
resulting respectively from heterogeneous and homogeneous
nucleation .... ere charanerized by X-ray diffraction, XPS.
RBS, and TE:\1. The compositions of these single-phase ma
terials are gathered in two main domains located in the
GIN> I part of the C-B-N composition diagram. It is
s.t:lled that the carbon-rich domain results from structural
disorder of an ideal C!B 2 N composiltion. The thermal beha"
ior of these films indicates that no mass loss can be detected
after I h at 1700C but a graphitization and a formation of
small amounts of BuC, are observed. Density and prelimi
nary electrical conductivity measurements were also per
formed. [hey' .... ords: chemical vapor deposition, solid
solutions. carbon. boron, nitrogrn.]
l. Introduction
T
HE simii"ritv of the crystalline structures of graphite and
hexagon:!1 boron nitride immediately suggests the possibil
:ty of obtaining solici solutions of these materials. Graphite
Jeing a blaCK ,emimetal and boron nitride a white insulatOr.
meresting adjustable properties could be
:,ectcd for their
Very lillie work concerned such materials
'.nd most syntheses v. ere carned out by chemical vapor depo
ition (CYDI. The first results on these compounds were pub
Ishcd in 19"72 bv B:!dzi:!n et uf.' From the reaction of a
'Cl,-CCL-H:-N: mixture with a carbon rod heatcd at
with graphite-like structure
obtained. The composition was not mentioned. C-B-N
laterials were deoosited in 191:>0 bv Diefendorf I!t af. The
nitial gas-phase aO.,-NI-I.-C,H: at high temperature
and under 101' rrcssure led to C-B-N comrounds
I'hich were ("O-rha.-.,: BN-C mixtures as revealed by lR
pectroscopy.
It was only in 1987 lhat Bartlett and co-workers rublished a
lapo:r'\ showing evidence of the e.xistencc of C-B-N solid so
ulions. which were studied from the point of view of their
Icel; ical conduct ivit y some time later ina second rub[ ica
:on_- The same rrecursors as Diefendorf were used with
vdrogeo as carrier gas rut the t..:mr..:rature rang..: of <JO{)" to
XJ'C was far j""..:r. .\PS analysis uf the black solid deposit
:Lowed the exi<tence ofhpndings hctween the three clements.
'1'.'0 compositions were h\' chemical analvsis:
""'jC""\0:,, ", and 8" "Cit ,.,''':" ". After annealing at 900-C,
Ie Xrav diffraction patterns confirmL'd the Iayer::d hexago
II SI ruct 1I re.
No. IW1S-IfI. 'h:':L'I."CJ Mar(h \I)lll. ;Irrn}\cd <.k[\lbcr 7,
.1 .
RS. iJ.fJ>liJolI 1\rril:.n.1n <. 'lk't. FLln..:\,.'.
OCC:"1 rc dt.:' I'.t'l"al. ..... 3hOO 1'1,.""':1':. Fr:l nCL'.
At th..: sam..: time. and starting from the same boron and
nitrog..:r. precursors but V.ilh various hydrocarbons (CH,.
C, H __ or C 2 H:l. Mnore 1ft af. ' ..' obtained sim ilar materia [s
betv.een 15000 and 190U'C under reduced pressure (07 to
2 torr). S.ome diffractograms of the as-deposited samples are
consistent with a single-phase mixture and chemical analysis
account for the B".'4C" composition.
:-Vlore recently, in an attempt to carry out a two-phase
coating of "8,C"-BN from a BCI \-NH ,-CH,-H, mixture
11::;77'C, 25 torr), Besmann' obtained a deposit.
.-\ES analysis revealed a composition of B"."C"'jN,, ".
C\'D is nOl the only way to rrerare such materials and
carbon films containing nitrogen and/or carbon can be gener
ated bv pyrolvsis of appropriate precursors as shown by Maya
Iff al.- Obtained from an aliphatic borazine precursor, t:le film
has a metaillic appearance and presents graphitic feat'Jres. Its
composition is B"."C,...l1NUJ5'
Even though their structure is IlOt graphitic. we should also
mention the existence of transparent C-B-N fjIms prepared
bv plasma-enhanced CVD from a 8:H.-;\H,-CH,-Ar gas
ph:Jsc by Yamada et af.
4
Various compositions are mentioned
such as or
All the compositions cited above. corresponding to B,C.N,
graphite-like structures, are plotted in in Fig. I.
This short review shows that information on C-B-N solid
,;olutions is scattered and rather scarce. This led us to under
take a more systematic study.
The method of preparation of our samples was the same
as that used by Bartlett et af.:' i.e .. CYD from a mixture of
acetv[ene, ammonia. and boron trichloride. but various carrier
(nitrcgen. helium, hydrogen) and a 'somewhat higher
depmition temperature. (900' to 1O.5()0C) were used. The de
tailed process and reaction are described else
where a, well as the niorpholugv of the deposits.'''11 Two tvpes
/i
c
I
.
0
E
0
v
8
'3
C2
L
B 8N
B.rtl.ll [3-4]
Moor< [5]
B"m.nn (6]
o M.
y
[7]
<:> C5 82 N
N
Fig. l. C-Il-N cllmr,,,il;,,n LJi.,sram. showinl; Ihe
h,)untl My pr-,:vll1US alHJ the.: JonLlln" of c..:xlslcncc (C
;lnu .. \) pf our 0\\'0
1(,1
..I

)(lurlllli of Ihl! .-tmeriuJtI Ceramic 50 11:1.1' - Sallg'lG .:t al. VoL 75,
162
llf materials wcrc obtaincd' verv mouth rhln (<I few lcns
of mlcromcters thick) rcsulting from a hetcrogcnc us rcacrion
on the sub51rate (graphite or ,iliel and gr::lnul:H ma
terials from a homogencous nucleation I n the phJsc. The
composllion, structure, and som' properties of both kmds l,f
materials Jrc presented in this paper.
Thc composition values givcn helow r'sult from chem leal
an lysis of the granular s (where \ulllclcnl m,HcliaJ
wa avaibble) and Xray microprobe an31vis ot the 0
clemcnts Other than C, B, N. nd 0 "'<.:r<: und in signifiCJnt
quantIties in the samplcs, but some hvdrogen may also be
prc:'ient since itS uctcction is alway. dlfflcull.
The structural studies were p..:rformed hy X'r::J:' dlfiraction.
Electron microdiffraction wa Iso uscd occasionJ Iv. A mOre
complete picture of the chemical bonds was obtained by
X-ray photoelcctron spectroscopy (XPS or" SC "). .
The stability studies were conducted In a graphite reSist
ance furnace. undcr a flow of nitrngcn up to 1700'C :lnd a
tlow of argon ahove that temperature The electrical rC.15t
ance of the films was measured by the four-point tcchnique at
between 77 and 300 K.
[I. Characterilation of the Film.
(I) Composition and lIomogeneity
Although the deposition for (he film;; was :;1
wavs 1000or lO50C. varying deposition parameters (e.g., gas
rate. gas composition, pressure. etcI could vl.:ld samples
wllh quite varied compositions. Figure 2 is a phot grJph of J
typical film, which shows a very smooth suriace. with a
strong reflecti !Iy. Thcre was no difficulty In obtaining good
re.sults from the Xray microprobe with such samples. At least
five different analyses were performed Jt different POintS of
eJch film and never differed by more [han a f'w pcrccnL The
oxygen content was always negligible. except in twO case.:
(one sample with 15% oxygen, one with :)'!<l, so that the com
position can e3sily be represented in a triangul3r diagram,
with pure carbon, pure boron. and pure nitrogen located at
the corners. Figure I shows the results for all of the oxvgen
free samples. Alimited number of tudies hy thc Ruthe'rford
backscallering (RBS) tcchnique and by uger elect ron spec
troscopv (AES) allowed us to conilim that the films arc ho
mogene lUS and th:lI. if any o,xygen is found. it is I aled J[
the surface of the samples (50 nm) and (:In be conSidered as
surf:! c pollutIon.
Two remarkable facts emerge immediately from an examl'
nation of Fig. I: the BIN ratio is grcJtcr than I and
quite often above 2. and the film comoosilions arc r<:stricled
to l\V mall domains. C and A (more h3n tiO% C:trhOfl in C
and less than 45 al.% in A), hoth "lIh Icss thdn:) al.'
naron. 11orcover. lhe compositions In domain C aClually tcnd
to gather around a "focal point" corrc.sponding aprroxlmalely
() 5 3 2 1.5
o {
Fig. 3. X-ray diifraction paltern of a malerial from d m:!ln
to b2.S al.% C, 2S at.% B, and 12.5 at.'/O , or ( .1 rl)
"f rmula" C,BlN. The C domain extends toward the bin
B-C composition diagram on which it i limited by l he Cl
positions BC
l
nd B 6 according (0 Banlett
H
(2) X-ray Dlffracrion
Figures 3 and 4 show typical dlffractograms f
from thc C and A domJins. hese diagrams are de. rly th
of solid solutions since they cannOI be resolved Into sepal.
diffracto rams of BN and carbon. But thev are suikinl!lv d
ferent from one another. Both types o(material c.xh;blt
graphitic turbo tratic structure, With no three-dimenSI nal c
der (unresolved (100) and (101) pc' ks). But (he C diffr:!
togT3m (Fig. 3) shows a strong intensity of the smal!-ang
scattering, while no such feature appears In Fig. -I. Similar!
lhe very wide (002) diffraction line and the d dlstanc
(0.363 nm) of the A material cOOlrasr with the short d valu
(0.338 nm) and sharp line of [he C film, where the carre
sponding coherence length. L
c
, can be estimated to b,
20 nm. These observations show th t. in contrast to the .:
films, the C materials have a welldevel ped two-dimensiona
crys:talline order. Roughly speaking the A depoSits 1In lfl
deed be ualified as "amorphous" and the C films as "crys
talline." As a maner of fact the two-dimensional organiz:lIlor.
"f the C materials i actually more c.xlensi e than that uf pure
pyrolytic carbons deposited al the same temperature (L
c
be:
tween 3 and 8 nm, and d
rm
from .342 to 0.346 nm) .. I' Il
even more developed than the two-dimensional Structure o[
gr<lphitiz ble pyrocarbons heattreated at _OOOc.
0) X-ray Phoroelectron Spectroscopy (XPS-ESCAJ
A good deal of caution is necessary when using XPS spc
Ira for a quantitative chemical analysis of deposits, since thiS
technique is very sensitive 10 surface pollution of the sample:;.
However, it is a very efficient [001 or detcrmining Ihc
of bonding involving each element. This is the wav wc used It
in the present study.
2 10 5 4 3 15
oI Al
t
Januarv
( "llil Til C1C!"I 21.J( ion oj C-IJ-N Solid .'.,,1/1 I ions Dl'pmllcJ (mm a Cas('()us Phase
163
BORON
B
I
NITROGEN
N
8" 'B
En.rgl (,.,,)
fig. S. X PS spectrum of pure BN. Flood gun = 9 eV.
The "normal" peaks of Band N in pure pyrolytic boroil
nitride arc shown in Fig. 5. Each consists of a single well
shaped line which can be used as a reference for the spectra
of the C-B-N deposits. When the environment of the central
atom (B or N) becomes more electropositive. the peak shifts
to lower energies, and it shifts [0 higher energies if the atom
is bound to electrone!!ative Similarlv. the
C line in graphite can be used as a refe(ence for the C spectra
in C-B-N materials.
Figure 6 shows the C. B, and N spectra of a typical C de
and Fig. 7 the spectra of a typical- A film. It is immedi
Jtdv obvious that these are not the spectra of two-phase
mixiures of carbon and boron nitride, which would consist
onlv of the BN peaks for the Band N atoms and of the C peak
of the C atom. The observed spectra are clearly composite
peaks for each type of atom. and they arc evidence of the
CARBON
u
u
1\
7 ,/ I .
u:' I '.. U
. '

284 4
EMrgl (,V)
U
<Xl
z z
BORON
1898 188 En",'!T l,v)
NITROGEN
t 6. ,rs specr rum 01 " m"f<:r"d 'r,'n\ J"01",in C 1:1""cl
iD = 9 cV.
C"'RBON
Entrgl (,V)
BORON
En"'gl (.V)
NIT RaGE N
En.,-gl (.V)
Fi/:. 7. XPS spectrum of a material from domain A. Flood
= <; eV.
existence of the C-B-N solid solutions. The C spectrum al
ways shows either a C-.. or a C-B component (or both) on
the sides of the main C-C peak. The B spectrum alwavs pre
sents a component with a shift of -1.8 eY on the side of the
BN peak and the N spectrum always consists of the main NB
peak and a higher-energy component (N-C) shifted by about
-;-.1.3 eV.
Table I gives a general description of these XPS findings. A
very interesting r.:::u.ure is the intense component of the B
peak shifted -1.8 eY from the B-N reference, which on first
sight cannot be interpreted from the available literature. It
must be remembered that in a graphitic type of lattice each
atom has three close neighbors and that the corresponding
XPS shift depends on the overall e1ectronegativity of this en
,ironment. A positive neighbor may compensate for a nega
live one. It is known that the B peak of a boron with three
S neighbors (BB,) is shifted -4 eY from the BN, reference
while a BC) peak is only shifted -2.5 eV.
11
A shift
l)f - 1.1) eV may then correspond either to a BCN2 or to a
I3NC, type of boron. most likely since il is closer to
BC, than to BN,.
We opted for interpretation and conclude that a large
proportion of the (,{lron atoms are surrounded by two C and
Table I. General Summary of
Ihe ESCA Spectral Analysis of A and C Films"
<:;. of hond
Ekmcnl anJ
type nl h<mJ Oomain 1\ Domain C
Boron B-N o 05 20-25
Bl'ron ., -1.8 20--:'0
Camon C-C o 50-75
Carbon C-N +0.810 + I.-l 15-25 5-25
Carhon C-Il - O./:{ III - I . I 5-20 15--45
Nitrogen N-I3 II 65-'X1
.' _Nitrog..:n.N-CR "'13
IO"':Yi 17--411
JO/lrnal of rhe American Ceramic Sociery - 511/1gnac ct 01. Vol.
onc N. with thc following grouping:
C
""B-N
C/
A similar led us to conclude that the nitrogen
peak on the high-energy side of the reference NB. peak cor
responds to a or a NBC, group ir located be
tween the NB, and NC, (+2.5 eV) positions.
(0$) Suggested Structures
The above results enable us to suggest structures for the
various films of domains C and A, more specifically for the
two-dimensional graphitic-type layers which constitute their
turbostratic stacking.
It is interesting to note first that, following a synthesis
BC,N by Bartlett and co-workcf1i. a theoretical study'h of
possible structures concluded that B-B and N-N bonds have
an inhibitory effect on the stabIlity of graphite-like layef1i. On
the contrary, a arrangement, as represented at the end
of Section Il(3), would not induce internal constraints in the
laver and would be quite stable. We accordingly looked for an
o;ganization of the C, B, and N atoms centered around such
C;BN groupings, with a BIN ratio close to 2 and a maximllm
number of stabilizing graphitic C-C bonds. The result of this
search is the following elementary
c
I
C...... C/B...... N'C
I I
C B
C../ ...... C/ ...... C
I
C
which is built from twO groups with one common
atom. This arrangement is compatible with all the types of
bonding which were identified by X PS. and the correspond
ing BIN ratio is exactly 2.
Figure 8 shows how this cell can be used for generating a
whole graphitic plane. In the upper pan of the figure the ori
cntatio-n of the BNB group is kept constant. while it is ran
dom in the lower part. Both arrangements correspond to the
same overall chemical composition, which was found
to be thc "focal point" of the C domain in Fig. 1. But changes
can easily be introduced in CIBzN-generaled struc.,
tures, which lead to slightly different compositions, either
with an excess of carbon or with BIN ratios higher than 2:
Examples of such changes arc shown in Fig. 9.
They may be called "defects" if the pure CsBzN
ment of Fig. 8 is considered to be the "perfect" lattice.
such ("primary defect"). illustrated in Fig. 9, consists'f:
of a nitrogen atom shared b three C,BN groupings. It i:J.
volves a local BIN ratio of 3. Another one ("ternary defect") ,
is actually a boron nitride microdomain (two N and seven '.
B atoms) included in an otherwise "normal" CjBzN lattice...
Its local BIN ratio is 2:33.
Many others can be imagined, and it is clear that all com.
of the C domain can thus be obtained. All of these
struclUres, which do not involve a lowering of the carbon COn
lent, should be reasonably stable, and account for the ex
tended domain of existence of solid solutions in the upper
part of the diagram in Fig. l.
It is more doubtful that such regular arrangements exist i;j
the A domain, where the carbon content is much smaller. But
the relative intensity of the boron XPS peak shifted at
-1.8 eV remains large (Fig. 6. Table I) and it is quite
likelv that the A films consist ohery small carbon and boron
nitride domains linked by numerous C,BN groups. In anv
case. Table I shows that there are no boron atoms with either
a pure carbon or a pure boron environment (no pure boron
domain and no boron-substituted carbon domain).
High-resolution transmission electron microscope observa
tions of the C domain samples confirm the stability of
as shown by the presence of large-scale (70 nm\
groups of parallel C-B-N layers, illustrated, for instance. en
Fig. 10. Such structures may be expected to "graphitize""
rather easily.
(5) Thermal Stability a"d "Graphitizatio""
The films from domain A arc strongly adherent and diU:
cult to split from their amorphous silica substrate. We were.
however able to detach and submit some of them to treat
ments at'higher temperatures. No mass loss was detected after
1 h at 1700
c
C, and a typical diffractogram of the resuillng
materials is shown in Fig. 11. It can be compared wilh lhat of
e
e
...
Fi/:. 9: . In " ,I I It" giapfliiii.: I.,v",'
"
-.
j
J
j. Cullan alom,
. 0 Huron ..
o i\ilroc.C'n
_.- -.
Ill5
January }l)'I2
J
Fig. 10. Lattice fringe image of a film from <.h)main C.
the :ls-dq;. sited film \ There is obviouslv crys
lallization ,nduced bv the heat trealment: a sharper I [J(2) line:
",ith a mL',:surable coherence lem!th (L
c
= 5 nOli. a reduced
Ii",: distance of U,]..J] nm. ant.! :J.- splitting between the (lOO)
and (lOl) graphitic lines. which is an indication of some small
three-dimensillnal organization of Ihe IJttice. But "eak lines
:J.rc also clearlv on the left- and right-hand sides of the
(100) graphite' [leak, They can he to some Iraces of
rhombohedral boron carhide, We can conclude thJt these
C-B-:'\ films arc panlv "graphitized" by heat treJtment at
1700'C. but also sho\\' the JppearJnce of a very small amount
of a B"C: phase,
The effects of heJt treatments on the sulid solutions uf the
C domain hJVC been more extensivelv studied. Some B"C
Jines appear in the 1700<C heat-treJted' samples. as in the c:J.se
of the films of dom:J.in A. and thev remain vi, ibk up to
From :WOO'C upw<lrds. the is <I mixturc of
:.lfhon and boron e:J.rhidc. resulting I'rom the reaction ot' COlr
bon and boron n;tride,"
It must he rememhered thOlt the a,s-deposited sOlmples <lrc
alreadv birlv \\ell t\\'odimensillllally crystallized IFig, 3).
There arc no ohvinus modificati"ns llf the graphitic compo
nent o! the diffraetogram ur to hut :1 very remark:J.hk
result is the comrlete graphitizatiLln achicvcd at a tempera
ture a, low as 2.'IHI"C. Figure 12 sh,," , thc variati'ln and
mass ILlSS llf the samplcs as lunctillils llr the he:J.t-tre"lment
temrLralure. Onl" ah,,"e 20(M)'C <ines a signifiC:lI11 mJ.SS l'lSS
OCcur, indie;lting the rrogressivc driving out of ,lnd
::::N 82PI
NO
"0
t"altd at liQO'C
."1- -;;;
o 0
1 5
II. .\-r:l\' Jillr;Il..:(I\Hl P;ll1Cfll ,'1.1 Ill:lll.,:ri:d frPIll Jpm,lIn /\
::eaI"'c;IIcd I'" '" 171111 ('
3 ur--------------------,
20

N
8340
..

'"

-",


10
3,38
2:
3 36
3 34 0
laxJ lam 3mO
HQ4[ (C)
Fig. 12. l\h"-Io,,s d ...: a funclinn of lemper:lIl1'c
lor he"I-lrcalcu maIer;;", irom domaIn C,
plissihly of some horon. Lllthough horon carbide rem<lins
present up to 25(K)' ,
These studies were e,'tended by high-re,olution electron
microscupy IHREM. Jeol 20(0), Two different microtcxtures
seem to coexist in s<lmples frum dumain C: the weU-developeu
lamellar texture (see Fig., 10) docs not change noticeably up t
2IH)()cC. wh i1e Sllmc small where layers show LI st rong
curvature :J.nd arc probably less graphitizahle, arc apparently
thc origins or thc horon carbide rhase.
lIS) Other Propertie'
The t.!ensity llf the deposits was found to he U;9 for the A
dl)m .. in and 2,135 for the iilms uf the C domain, Such high
\'alues arc a confirmation of the ncar-absence of micropuros
itv. which was ohserved bli transmission electron microscopv.
fhese as-deposited solid ,ulutions arc denser tha'n
both pyrolvtic earbons'- and pvrolytic boron
t.!erusilcd Jt Ihe same temperature,
Preliminar\ electrical conductivity measurements were per
furmed on so'me films betwecn 77 ;nd :Ion K. The small size
of I hc samples precluded accurate measurements and a 20%
error margin seems like"', The room-temperature "alues in
erea.se !'rom .' tl) 10" n-' ,m':, This is in t he range expected
for carbon deposited or heat-treJ.ted at 700
0
to
'tIH)'C. Figure 1-' shows an obvious correlation between these
results an'd the carbon coment, hut this rnav not he due onlv
to thc direct influence of an increased uf graphitic
l11:J.teri .. I, The fact t!lJ1 the deposits of the C dllmain arc more
conductive b\' at <I factor of SU and often a bClor uf 1000
th.. n the f\ samples is Llhl certainl\' the effect of a hetter
C[\'st;llIine or!.!anlz:J.tion. All the samoles show a conducli"itv
If in<.:rea"ing temperature. The (f vs liT pluts
Cl1Osi,t of t\LCO straight-line s.:gments. suggesting both an cx
Irinsic and:J.n intnnslc scmu:onductivity. The energv gaps arc
ill {hL' Ill" to 10': lil1trin"ic) ;lnU III ' 1" eV lex
!rin'icl. :s::, CllrrelLltion was observcd hctwcen thcse " .. Iucs
.1I1d thc comr,'sition,
This prclil11il1:J.f\' ,(ud" " ill he cl>mpleted hy a more system
.liic c.\;lmil1;lll11n of thc g:d\anumagnelic rrorcrtlcs of these
",lid ,,,lUI ions, Hll\\'cvcr. our conductl\'ity resull' In alre;luy
6

E
4

C
2
:Jomoll''l d
0
0
C
.....J
-2

0 20 30 40 5(] 60 !O
C.rban content (%)
IJ_, 1',ln:I,;,',,1 l'\,"dlll'1;\lIrl,r:c.-n Itll1l'tllln "I
tlh.."lr t.II"llfl t"t\llll"/ll
'.
. ----j
1M }ournul of Ihe American
be compared wi t h ot her.; pubIished by Moore and coworkers.
Will se C-B-N materials were deposited netwcen 1500
0
and
19DOC. The observed room-temperature values an: about the
same order of magnilUde and increase in the same way With
the carbon content. Similarly, their samples usually presented
a slight increase of conductivity with temperature.
Ill. Characterization of Granular Materials
(1) Composition
Several types of materials were obtained frum the nuclea
tion process in the gas phase" at9Q() to l000C. But only th c
with the higher carbun content (> 7OC!C') , which show eviden e
of being truc solid solutions of carbon, boron, and nitro' en,.
are examin d here. The compositions nc the correspondlf1g
experimental parameters are Ii ted in Tables II and [I!.
Though the oxygen content is not always negligible. it IS
sometimes convenient to exclude it in the determination of
the carbon. boron. and nitrogen percentages. The values com
puted in this way are also listed in the table (% %BO, and 0.
%N). All these CO-Bo-N compositions are located in the so
called "domain C" of Fig. I, although these granular matcrlals
are not always as well ordered (sec below) as the correspond
ing films, and they all show a noticeably higher carbon content
than most films. The "idea'" romposition is conspicu
ously missing. .
The oxygen content probably originates rom the exposure
of the materials to air after their deposition, and the
most likely cause is the absorpti n of W:1tCL 'incc poorlv
crystallized boron nitride is known to react stron.ly with
water vapor. II.::
(2) X-ray Diffraction
(A) As-Dcposiled Samples: As already pointcd out in the
case of the films, the diffractograms of the gr:lnular deposits
are not a superposition of carbon and B diffraction speclra.
These materials are inde d solid solutions. We observed two
types of X-ray diffractograms, depending on the temperature
of d .position (T
d
) of the samples.
At T
d
= IOOODC: The typical diffractogr m presented
in Fig. 14(a) shows that the deposit is fairly well two
dimensionally ardercct. Wilh a sharp (002) line, a dIU: distance
of nm, and a coherence length L< ot about 4.5 nm. But
it i' still a turbostratic material since there is no indication of
a srructure in the (!O) peak.
It is quite interesting to compare these results with thear
responding values of an acetylene black (T
d
about 1300
4
C):
d,m = nm and L, = 2 nm. Simil::!r1y a pyrolvtic carbon
erumic Societv - 5uugnac el ul.
Vol. 75.
depositcd at lOOO"C shows the same order of magnitude
which'
of to'
but a sli!:\htly d,,,, (0.346 nm). It must be onclud
that the granular C-B-N materials :'Irc better ordered than
the "pure carbons" deposited in the same temperature ranl!e.
Thcy bear some resemblance 10 t he films f domain
arc also deposited near WOO (see Fig. 3).
AI T, = 900C: The depo its a n: very poorly crystallized'
and can re:!lIy be said to be "amorphous," as shown by tbe,.
typic::!1 diffractO ram of Fig. 14(b): very broad bands and v iI
large d'Jf2 distance (up to 0.37 nm). -.:...
(il) Heal Trt!atmenl 10 1700C The diffra tog ms
Fig. 14 are those of dcp sits with very similar omposilionst
(see Table Il) but differ nt T
d
After heat treatment for 90 mID )
at 1700C, their diffractograms are those presented in Fig. 15. -.
The material deposited at ICOODC is practically unchanged, but ''':
the 900C-deposited sample shows a striking structural im- ;
provement and an obvious two- imensional development of--:.
its rystallinity: the d"'J2 dist nee dropped to 0.343 nm and
L c value grew to 3 to 4 nm_ The effects of a lower deposition
temperature :Ire almost rubbed out. .;
Figure 15(b) also shows very weak di (f.-act ion lines Jt 0._56
and 0.237 nm which arc' sstgned to boron c3rbide.
lines are particularly visible for samples of high BI,
and I w Td I
It is also interesting th::!t heat treatment to 1700
D
C t
Out most of the a sorbed oxygen, with a weight
10. s of 2% to 6%.
(C) Heal Trealmenl above 1700C: The I. suits presented
above show that the graphitic C-B-N solid solution struclUre
remains S'table up to 1700C. But above that temperature the
formation of boron c:lrbide and the drivlf1g Out of nitr gen are
Iikelv to occur, and a mixture of graphite and boron carbide
might be the end product of the heat treatmenlS. Figure !6
shows the evolution of two identical deposirs (46 P3 and
-l P4) when heated t :2000C and a ave. The X-ray diffra .
lOgrams are indeed those of mixtures of carbon and bor n
carbide at 2000C. The carbon graphitization is nearly com
plete at 2500
D
C, with a well-developed three-dimension' or
der and a dim distance of 0.335 or 0.336 nm. The e small
values indicate the presence of boron as Ire dy observed tv
\100re ct al.:
J
It is also interesting that. afrer hear treatment at
2500C, the more amorphous as-deposited material (-l8 PJI !
jiclds better graphitized carbon while the more crystalline as- f
deposited 46 P3 shows no trace of bor n car bid . In bOlh
cases the weight losses at 2500C are quite considcrnblc. on i
the order of 50%.
Ali of these results show that heattre:lImenr effects on the J
stabilitv and behavior of granular C-B-N solid solutions 3re
4
.
Table II.
S.mpl< D..:p h::mp (fiC)
r;r
2J loon 90 7
24 \)00 Kl I:'
25 900 So 12
37 P3 900 01 17
37 P4 <JO() 73 13
46 P2 lOOO 77 10
46 P3 1000 7 10
40 P4 1000 ::16 7
4f, P5 1000 SlJ h
-IX P3
l)(){) tiS 1(')
-IS P4 9llO II
4S P5 9(lO 74 12
00 P3 1000 til III
/ill 1'5 WOO 'c!,7 I,
hi P2 1000 6X 1-1
ill P:l !Om XS
i,:; P:2 I(Xl(J 7.'\ II
i,:; P:; 10m XI) I,
(,1 P4 llXXl .. 7
?' .. h.:r/:-J.. ... 11ll!ll'.1ll: Ih.ll .... l'rnr0'\'llllt1'" Wl,:rl.: d ....-llrnlll1l'd It"n, llh """Ct.1I
r;.c
J \)0 7 J 233
5 :2 l:S2 ]J
5 _.34
2 '0 12 ? 6
IS 7
6
17 107
13 I 73 13 13 1
9 4 79 11 10 1!2
7 6 82 10
g 1.3
7 l:l6 7 7 IU9
:;
2 lJ! 6 3
13 3 70 16 14 121
l)
!lO It
<)
1:0
9 5 71' 12 10 l.J()
6 3
l{4 l() 6 1.54
.1 4 l)()
7 3 2.10
11 7 71 15 12 1.25
-\ 3 ':II 5 4 lAX
X 3 HO 12 'i 150
(,
]
2
..,
SIi
')(1
I,
7
11

Ill]

1\." '''I.II
ClruTactt:'ri z(J/ioll of C-f! -,111 Solid 5o{/ltion I" Dt'{)(}rtt -d (mill 11 (;l/sr'O/lS I'I/llsc
Table 111. Experimental Paramel it iun of Samp,,"s able II'
S"mplc LJ I,
Flow rale (Uhf
"H, C,H,
TOI J I (I..'
tP,,)
T.... mper;Jlurl."
(C)
Id
Il'm)
-" _.J
24
_5
37
.1/\
-18
60
1.35
1.35
1.60
1.35
1.35
2..()U
1.35
1.2
1.:2
U
1.2
1.2
I.
1.2
1.2
12
12
12
I:'
1.2
1.2
26(X)

_600
26()()
260u
2600
26UO
1000
(J()n
':100
':IO(}
IOO(}
'-J(}O
1000
10
j(1
ill
I
I
I
I
61
63
1.35
135
1.2
1.2
12
12
2fiOO
2600
1000
l(X)()
!
'G' I' Inc (0 (he hOl lone: cntrOlnce of (he {(,... xl ... 1 p'pe C':Jfl'yin!! NH 1. S.J.mc dflutllln In nlll'OCCn lor "iamplc:l'Io 2J. 2.-1.. 25. 1, -Lh. JnJ .1S.
l,"llum 31 a rt'."tldcncc: time for (0 .::: fll)"" 1';11<: 01, the c;Hrlcr S:l Illow r.H<: ()f (hI,." rcaCl''Yc f'1: Ie,).
ery similar to the effccts on films_ They all acquirc a fairly
ood two-dimensional order at I700C. yield a mixture of car
on and boron carbide al highcr tcmperatures, and it IS very
kely that the easy graphitiz':llion of all of thesc deposits at
as I w as 2500C is an illut rati n of the CJl.:!
,ti effect of orono Marc specifically, the
ranular samples bear a strong resemblance to the films of the
\ domain deposited at 1000 or lOSOC. and the behavior of
11' granular mat rials dcposited at l()()()OC is quile closc lO
1at of the film5 f the C domain, also depositcd at IOOOC.
1) XPS Study
Two typical XPS spectra. arc shown in.Figs 17 and 1,. As
1 the casc of the films. the environment of each B. C. r
lOrn can be seen to be quitc No single NB or
'" a
a Td: 1OO0C
A6 P3
L
c
: 45 J,
'"
9
. a
'"
'"
':!
a
0_ ;;;
5l
U>
'"
0
iii '"
wi ('.i '"
-
0
0 (Al
(a)
Td : 900C
48 P d

l2 le
'" a;
0

'"

",'
",.
ci
'" '"
0
{!j
(b)
peak and these spectra obviously belong to solid
so!U{ ions. '
Since X-ray pholoek.ctron spcctrosc py is mainly a tcch
nique f r nal. sis of the sample surfacc. and since oxygen
absorplion by the granular deposits is fJr from negligiblc.
promlncnt 8-0 and C-O peaks might be expecled in the
spectra. It can be seen [hat the peak. shi tcd ab Ul
+ I eV from thc rdcrcncc graphitc pcak. is r lher weak. while
the 8-0 peak is very conspicuous. This is a confirmation that
most of the absorbed oxy_cn corresponds I lhe f rmarlon i
boric xidc or acid.
N-C component, on the highcnergy side of the ref'r
cne NB peak. alrca y observ'd In the fjlm spectra.
It acCOunts tor approxlmatcly one third () the [01 I N inten
sily, and agrecs well with the previou.ly suggested ( ,

The small. -N Ill] C-8 shoulder.; on bOl h sides of I he car
bon pe k show th t :Iloms are mostly linked to [her , but
t hat some of t hem arc 31so bound to eit her B or N.
The (-J eV) component of the B spectrum is quite in
Icnse and confirms the similarity of these gr2nul.:n
Td: l000'C
'"
a
46 p)
a
c;:
0
T

r!
9
0
\0 5 4 2 \.5 1
o (!)
(a)
'"
,..;
Td : 900C
;;;
0
<18 P 4
0
:30-<l0!
T
Q
':!
L
c
;;
0
1.5
(b)
Ie, 14_ X-rav Jiffracti"n rallern, of p"nul;Lr
Fie. 15. uiffr:lclinn p:ltlCrn,'\ 01 gr,lIl1d:lr m:lfl..:ri:J1;'\ hl."al
..terlal,. lrc',ll<:J ;,\ 17IH!C .
Ill!)
JOIlTnal 0/ Ihe Amaican
4G P 3
T
d
: 1000"C
I

1O 5 2 I 0
(a)
;1 3
HTl : 25OO"C
II
10 5 2
o (AI
(b)
.
P 4
Td : 900 'C
HTT : 2000 'C
(c)
48 P4
HTT : 25OO"C
\0 5 2
(d)
Fig. 16. X-ray L1iffraction palterns of luonulor m;lt rials heat
Healed succes" velv ot 2IlUO and 250()QC.
with thc films. Our previous inlcrpretation rcmains
v;did and wc assign it to a C!N cnvironmem of the B :Ilom_
An interesting difference with the films is the mther stn ng
low-energy componenl (ncar -4 eV) of the 8 spcctrum. It
corre:;ponds 10 B-13 bonds and is an inJic:ltion of a nonnegli
gible proportion of boron-surrounded B ;Homs. that is. of
homn isl,lnds on the m;ltcrial.
We may cl1l1clutle from these XPS rcsults that thc
arc solid C-l3-N solutions. "ilh some
horon oxides. dnd that (I) boron is mostlv hound (0 C;lrOI1l1
and nitrogen in C,3N groups. similar 10 those which consti
tute the film structures. (2) nitrogen :ltoms arc hound
10 one C and two l3 ncighbors. and (3) some horon islcts exiSI
in the hulk of the solid solution.
Thc st rueturc of these matcri,t1s is 4ualilallvcly
simtl,H 10 that of the C films. with the aJdition<Jll:ocxi.lencc
III huron nuclei. The l<Jet that Ihc "idca'" e.:lImpo'iti"n
not lound ,n JcP[)Sih cCrl:til1l" JII IIHlic:tllllll III ;1
l1lore.: widesrre.:;,d sl fllct ural u
crumlc ,),'0 ?I}' - SaltgnQC CI af.

398
Ent"l! \.
I
I
-- - --.:-:.'-:..:..: -+ _..., ------i
u
,
u
CARSON
<Il
z
BORON
<Il
u
cD
a
z
I
,
<Il
,'r
, I '. ,: I ... :
, I " "
':;< I >:. I /\
. -- -. - -. - - '':1-:''- .'+ ._. _
1898 188 (,V)
fig. 17. XPS spc:crrum of granular materials Flood _un = '-! e\
Z
I
NITROGE>;
cD
c-c
CARSON
284.4 (,v)
BORON
0
z
I
cD Z
cD co
U
cD
C/lllrtlCI<:rt211(IIJI/ 0/ (-/1-,\ .\,,//(I S"//I/'Ol/\ /)'"I/(I\I/"t/ (mill 1/ (;",",'(1/11 /'/111.\,. IAlJ
IV_ .. n
New nlJteriJls h":Cll "hl"int:u ", dcn'L'_ \Il1IHlIh film'
hy [h CVD in [WO uomJln, of lh,' '-l3-.
lion dlJgram. The c;Jr!Joll-rich uom;lin ..:.xhil)lt\ J graphitic
{urbOSlrJtic SlruClurc wilh ;] welldevcloped I \\,0-0 I fl1en -'lln;J1
crvstalline order grc;Jler IhJrJ gr;lphltizJhlc pyrucJrh n\ heJl
(rcJted a[ 2()()(JC. These depmi[.' arc ,in"lcphJ\e rr.;\lcriJI,
and the existence of honding, buwe<:o JII- of [he ekment\ is
confirmed by XPS. The c;mposition oj lhoe film\ i\ de
scribed hv thc C.B.N slOichiom..:trv JOu
tural disorder can for the eXlslenee of; L!(lm;JIO 01'
solid so/ulian_
The much poorly crvstailine solid SolUllons corre\pum.ling:
to the lower carbon content domain can be con\ldLf d In
of [lhe basic structural units JS the C.8;' films.
B th I\inds of materials exhibit behJvior "Ith re
spect to heat treatment. No mao s los\ i.'
at 1700'C and carbon graphitizatiOn ctlmpk!c at 2500'C. A
solidstalc reaction is rcsponsiblc for the driving out of nitro
gen above 2000C leading to an cnd OroduCT which 1\ ;1 miX
ture of graphitc and b,)r<;n carhidc. .
Granular deposits of cJrbon content coulL! ahu c nl .
tained by var\'ing the CV D r:lrarnctcr\. Although poorly cry\
IJlline, [he:, have Jnd pmpertles \Omewhd! "mtlJr
ttl the carbonnch films.-
Acknowleogm n15: We He \'0" !,,,,,dul Ii\ Dr CL,uJe lJuCl 11'.11'
r\qull:llnl::-.(jrnup-cmcnl lfe Ll1cq who rh.:rhlrmeJ rrh...\I'S
\1 dll.:S :.Jnd heine-d. wlIh Pro Tr.:Jn Uuc 01 Inl\"(:,r\lI\ cbudt: tkrnJrd
,L,'onl.!n lh..:ir' .
References
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C'I:V. L'T. Aprtl 2-l-:n. E ilc.:J F.A. Gl:t... kt. -
"'CIV. La GrJnec Park 1L.
:5. H. -anu . J. Dlcl\:nJorf. l'rqrt.:rlll..'\ 1)1 lhl: ... tLn1
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Rid:'. 11, f I",nfl').
ll. Kuu"'c(Jkis. T. ..du. C' Shen. R. t-LJ';I\loJr:.l. ,\1 Ll:rn...:r. f\: \\ I\.rl"II'
Il.tll .lIlt." H,!Jlkll ":'ll\d ,\ ... p.. ..t ... ul (,r,lrhll\: !nl..:r(.JI.JlllIn h;! I'/llllrffh':
.In.] f IUI\lllh; .. ..Iud It.:\,.. UI ;lIld HIt /1'J on Illl..
(d.q1I11IL- .fl.., ..\II/d,. ,\1n.. .'-1. (lllfi41.
\ \\. \1lJllfc. S I. C; t. I)llii. M S. I rc,,,,,,rh.tU". I. L
(. \\. lltl\.. ... , 1 P 1",1. find L_ Plr;'H1\. "Pn'rt.:r1I' oInJ Ch;lf.Jh.:rl/;llt,ll1 'll
(1IJl.pq'llL:U !1l1rlln Hfllk ,I".J C.lrhon .\blcrt,d, - J .-lfJP! I'f,\{ 65
'111'1 1:'\ 11"""lr
. J .\1 Lk,m;lnn. Chl.:nllc,d \,Irtlr f),,'rhl""11111 In lhc B,H,mt ... ff'l'fl
..... .-1/1/. r:lrdfl' jJ!:"\ 2-1\)M-'1111 tl'II)lll
'1. \1.\\.1 ... oJ L ,\. H:ttrl'. 01 ('on
1.1111111' 1lllrO{!cn .lnJ:of Bnrpn," J 1", (Ojl11'- .'w/(". 7.' (:]14/:-11'\ flll'-I(l)
., \\ ,\10Ilft,:. ''')lrucwrt: .1nJ rr\'[><..:rl'L:-' III Coll,,'rH1\IICOt.! PI1.' antJ
rnhtl(" ( . rhon . p. In PH)Cl.:l:OlnC\ or the IXlh Blcnn, .. 1 un
\\'or",.:"...:r. ,\tA. lulv 1")-24. -!lJX7 EJlh:d h\ P 1\ fhrtl\Oo\..-r J\m..::rl
l.lfl '",Irho" ,\Ll,'....... P,\.
1 I.Ho;.I\.1.J . .\l .JnJ t\.. lmpro... ..::l1Il.:fll\ til' Sire",'
( 1/l1folldhdll\ ..lnd Kt:"I",;,tIl('1.: tw l."hurl In Be r\jl"l :"01
lilli' I tlt.li(ud1t:J1I ..'iofo. IJi Pl II'l.J
t
}()) ..
"'1 S.,ucnoJc :tnJ ,\ ,lrch<.lnd. -:I\hotll the McChillll\m\ InvlJ"q:d In the.:
(-llic'ml",.d V;lrhH /)C'j"lll"I(lnn 01 (.',lrhon-ll(Hlln- 'l1rrt'cn l.nmpoun(h
I "een and IINNI c." C Ii. Ild,,1 S,-onrr.' ,I, ".I ""(. JIO [l J -'Ie (IY'IUI.
"( F. ;lnu 1\. C.JrMon-BtH\ n-
C"mr"unJ, Uhl",noJ hClwec'n "nJ IIHKI-C h, LPCVO" rp 7111-1/\ In
PnICCl:l.llng\ ttl Illh ..t1 un W;\.
()clllh..:r jl/\}IJ. Edllt:J h:v G.\V. Culkn E. SpeUf Ekctrncheml
I.:d r'l..:nnllll::!lllll, N1. It)LJO
i\ Jnkll rrl\atl.: communIC.1lion.
r (1111. Th.... ,I .. Ht)f(.lc':w"( 1 Ln,'>'cr'll> 1t.J7" .
.p Lllt'J'. 'lll:"I" l3"nJc:Jux: I 14:-\7.
Of lJ \"'-<.Ic.nl:r \"'. 1 RICe. . E. 0.1 v1'... J. I Mllu!c!l.:r. i-I;.JIldhook vi
.\ru\ l'IIIJIf'd;I,,'/ftlll ditcJ G. E.
(l,rr E.U..,;n Pr;llflt: . .V1:...J. 1474:
. Y Liu. R '\1 \l.I...:nll,CO\IICh. <.Inu M L_ Cohen. "Alomic .-\rr...tnccmcnl
.,n'; I:1.=,,, "n10 SITU"IUrC "f Be,N - 1'11\\ II,, n.
'p PJ,,'::;.d ..\\ .... rr({}[(j('VIl.\fulual Cht'l1Iu"!r\. Vul VIII. p. IU.\3. M.L,sun.
P.Jrt . Fr.Jncc. 1\Jh.'\
" . P.lcJulll EJ.1. II. rr. POJris. l'1faj.
"r \1 I.f.I '\uou. '\. lfirll\uki. unJ T. Hir:Ji. :In-J DL'pCl'S1110n R:ttc (''ll
heOla I.\;,epour-l)..:po IlcJ B,unn Nilnu.:_ 1. ,\1,.11;'" So.. 1.1.511\;- H t
''i. P. ,\r\';J antJ, "Prq);JrulIOl1 dnLl
II! l)orun. IIrIJc: r/':tn r"lfl .XsI/d F,t/n.,. IS7. :2(17-.::,
'. r .\f.Jl'uda. "SI3hdllv In (or Cht:mt :Ill\' :JpolJr
(31lf"t111 r"rIrIU-,:.) \tura ,kl., (7J (J'tXl,ll.
J. "CVD Boron 'rtndt:: Inll!tr:Jlion or f-lhrou'::l Structure.
Pr"r-.:rLl":' 01 pp. "&00... 7: in Prnct:cdl' I,) 'he.
Irll..:rn,t1 I(..'n;,tl CVD, nn"don. MA, 11.1-; ElIllrd h ...
C F. \\'.skcfh.:/J :Ino 1 \1. .
. \ \\ L SIron!!. G. L. Doll, "oJ M . Dressclh:Jus. -Therm:;&!
St:lhrlltv ul CU.' Cdmpchllt.:s"- rr. :,tJ-l in b
"Ir.n:b_ 1"1lh Rlc::nn..ll CtJnlcrcncc on C.Lrhnn. Pl..:(lil:'-\il\.IIH;,t Stale linl ...
.:':.'- iO, ItJ;'1J P \. Thro..... C:Jrhl\n
')1. \1.1""_ 1.1,\ ]1.1 ..... 1J [)
\'
!l