ELSEVIER Journal of Nuclear Materials 231 (1996) 151 - 154

Letter to the Editors

Erosion of amorphous hydrogenated boron-carbon thin films

A. Annen, A. von Keudell, W. Jacob *
Max-Planck-lnstitut fiir Plasmaphysik, EURATOM Association, D-85748 Garching, German3,
Received 10 May 1996; accepted 22 May 1996

Abstract

Amorphous hydrogenated boron-carbon (a-B 1 xCx:H) thin films were prepared by radio-frequency plasma-enhanced
chemical vapor deposition (RF-PECVD) using CH 4 and (B2H 6 + H 2) as precursor gases. Composition and density was
analyzed with ion beam analysis. The films were eroded by hydrogen and helium electron cyclotron resonance (ECR)
plasmas. The ion energy during erosion was varied by applying an additional rf bias to the target electrode. Erosion rates
were measured by in situ ellipsometry, a-Bt_xCx:H films with a carbon content of 15% were shown to be most resistent
against erosion with hydrogen plasmas. In contrast, pure a-B:H films exhibit the lowest erosion yield in helium plasmas.

1. Introduction to their composition and film density and eroded with

Boronization, a plasma-enhanced chemical vapor depo-
sition (PECVD) process which is used for the deposition
of thin hydrogenated boron/carbon or pure boron films on
plasma facing components in fusion devices results in a
significant decrease of metallic, oxygen and carbon impuri-
ties in the plasma and led to a significant improvement of
the plasma parameters [1-3]. As a consequence of
boronization, the regime of very high confinement (VH-
mode) could be achieved [4]. Despite this benefit the
physical properties of those amorphous hydrogenated
boron/carbon films and the influence of film composition
on erosion are not well understood. Initial experiments
were carried out in the late 1980s by Veprek and co-workers
[5], who investigated the erosion of BxC films with a
hydrogen plasma at 620 K and floating potential. In these
experiments, neither the whole range of film composition
from a-B:H to a-C:H nor the influence of ion energy on
the erosion yield were investigated. However, for the
discussion of the erosion of the first wall in fusion devices
these parameters are essential.
Thus, in this work a-B I_xCx:H films were deposited
systematically over the whole compositional range from
a-B:H to a-C:H. The films were characterized with respect
* Corresponding author. Tel.: +49-89 3299 2618; fax: +49-89
3299 1149; e-mail: woj@ipp-garching.mpg.de.
hydrogen and helium as a function of the ion energy. The
dependence of the ellipsometrically determined erosion
rate on film composition and ion energy is presented.
2. Experimental procedure
Hydrogenated amorphous boron-carbon (a-B j _ xC x :H)
thin films were prepared by capacitively coupled 13.56
MHz radio-frequency (RF) PECVD. The detailed descrip-
tion of the deposition apparatus was given in a previous
paper [6]. A mixture of 10% B2H 6 in H 2 and CH 4 was
used as precursor gas. In order to adjust the B / C content
the partial fluxes o f B 2 H 6 + H 2 ( F B) and CH 4 ( F C) were
varied from 0 to 10 sccm keeping the total gas flux
(/'to t = F B + F c) constant at 10 sccm. The whole set of
deposition parameters is shown in Table I.
As substrate material we used p-type single crystalline
silicon. The film growth was controlled in situ by means of
a H e - N e laser interferometer. After deposition the film
thickness d~ was determined ex situ by a Tencor Alpha
Step 200 profilometer. Together with d~ the index of
refraction n can be calculated from the interference pat-
tern. Film composition and atom densities were measured
by ion beam analysis [6]. 2.6 MeV He + elastic recoil
detection (ERD) was applied to determine the hydrogen,
2.6 MeV liB(p, a)8Be nuclear reaction analysis (NRA)

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Pll S0022-311 5(96)00389-3
 152 ,t. ,4nnen el al. / J o t m m l q f Nuclear Materiol.~ 231 (1996) 151 -~154

Table I 104q~ . . . . , . , . ,
I1:::t_ +. total density C + B
Parameters of deposited a-B~ ,C,:H fihns
Parameter Value 8- ""a+
"'., + ~ . . .+. . . + , '+ . .',o-
! El",,,, --. + . . - " / /
Precursor gases B 2 H ~, ( 1()c/~) ill H , . CH
RF frequency 13.56 MHz
'~ 6i boron~'D .... carbon //
Total gas flow I 0 sccm
Total gas pressure 2 Pa
RF power density ().(~5 W / c m :
4-' hydrogen ........,;./O"
DC self-bias 235 V ,v ~k.--.---/,,-----~/H ~':',~--~-........ ZX
Substrate temperature 330 K
Film thickness 125-150 nm "~ 2 - / "'C1
O~ "L
O ",
........ 4
20 40 60 80 100
OH 4 - flux / total flux ( % )
for the boron and 1.5 MeV H ~ proton enhanced scattering
Fig. 1. Dependence of boron, carbon and hydrogen atom densities
(PES) tot the carbon content.
on tile fraction of CH 4 partial flux F c in the total precursor gas
Films were eroded by hydrogen and helium ECR plas- tlux I;,,,.
mas and erosion rates were determined in situ by ellipsom-
etry. For a detailed description of our plasma reactor and
ellipsometric setup see [7,8]. The plasma is generated by the density of crystalline boron (13 X 1022 cm ~ 2.34
microwaves at a frequency of 2.45 GHz and a magnetic g / c m 3) which is a typical value for mechanically and
field is applied to generate the resonant field of 87.5 roT. chemically stable a-B:H films [9]. The carbon content
To allow a comparison of the ero,~ion rates the plasma
increases monotonously with I"c up to a value of about
parameters were kept constant. The gas flow was 20 seem, 8.3 x 1022 cm 3, which is also typical for hard and dense
gas pressure 0.5 Pa and absorbed microwave power den- a-C:H films [10]. The hydrogen content remains constant
sity 0.01 W / c m ~. The base pressure is about 10 4 Pa. at a value of about 3.3 x 1022 cm -~ hydrogen atoms. The
The plasma is confined by a metallic cage inside the total boron plus carbon density (hydrogen atoms are not
vacuum vessel. A plasma beam is extracted through an considered here) decreases with increasing carbon content
aperture on the bottom of the cage and impinges on the
with a minimum density for I c = 80%.
sample, which is mounted on a if-driven electrode. Thus,
All fihns presented in Fig. I were eroded by hydrogen
the production of ions and radicals in the plasma is decou-
and helium ECR plasmas. The kinetic energy of the im-
pied from the sheath potential at the sample. By means of pinging ions was varied from floating potential, corre-
an additionally applied rf field the kinetic energy of the sponding to about 15 eV up to 200 eV. The dependence of
ions impinging on the films was varied from floating the erosion rate on the carbon content C / ( C + B) of the
potential to 200 V dc self-bias. At the low applied pressure
films and the self-bias UsB is shown in Fig. 2 for erosion
the sheath is considered to be collisional free, so the
with hydrogen and in Fig. 3 for erosion with helium. The
measured self-bias corresponds directly to the ion energy. erosion yield depends strongly on the carbon content as
The ion energy at floating potential is estimated to be well as on the ion energy during erosion. In all cases the
below 15 eV. The temperature of the electrode is measured
by a thermocouple in the substrate holder. To obtain good
thermal contact between the samples and the electrode. 0.3 ' '- " ' ' ' " '
colloidal carbon was used as bonding substance. The sam- -V-%=2oovl ._.~ . ~
--A--u~=~oovl ~ ............
ple temperature during the erosion process was between 0.2 --O--U~= 5ovl .5~ C
320 and 400 K depending on the additional self-bias /Jstv

3. Experimental results and discussion •

i 0.05
"Vv ,, -
,. <, ..'/
, ,' ,

0.04 ",,, zx-- ~..~: - ~

a-B I _ ,C ,:H films were prepared over a wide range of
compositions with x varying between 0 and I. In Fig. I 0.02 b~" H2plasma
the boron, carbon and hydrogen atom densities are plotted 0 2'0 " do ' 6b ' 8'0 ~ 8 0
against the ratio of CH a partial flux 1~(7 to the total flux carbon content C¢(C+B) ( % )
I;,,~. With increasing CH 4 partial flux Uc the boron atom [:ig. 2. Erosion rates of a - B I ,C,:H films in hydrogen plasmas in
density decreases nearly linearly, starting at 9.4 × 1022 dependence on the carbon content C / ( C + B ) in the films and the
cm -3 for pure a-B:H films. This density is about 73cA of dc self-bias UsB.
 A. Annen et al. / Journal of Nuclear Materials 231 (1996) 151-154
0,3
He plasma ,~E.
0.1. /-V ~7"~',~" -
,??--~, zx z~''.O'° ........... ::,
0.03 g.,v~ ....o o D ~
0.01-
o oO-O U which is well known for graphitic materials [15]. Surpris-
[]- "
S --A--
vu..
u~ =~oov
0.003 _ 13/ /--O--L~= 50V
n_n u- L--D--~=,=
0.001.
0 20 40 60
carbon content C/(C+B) ( % )
Fig. 3. Erosion rates of a-B I x C j H films in helium plasmas in
dependence on the carbon content C/(C + B) in the films and the
dc self-bias UsB.
erosion rate increases monotonously with increasing ion
energy. The carbon content influences the erosion rate as
follows: Eroding the films with hydrogen we found a
minimum erosion rate for a carbon content of 15% which
is clearly visible at all applied ion energies. At floating
potential a maximum erosion rate for hydrogen erosion is
observed for a carbon content of 71% while at higher ion
energies this maximum is at 100% carbon content. The
maximum at 71% also shows up at all ion energies for
erosion with helium. In general, the erosion rates of pure
a-C:H films exceed those of a-B:H films by a factor 2 - 4
for hydrogen and helium bombardment. The only excep-
tion exists for helium bombardment at floating potential,
which will be discussed further below. A striking differ-
ence between helium and hydrogen erosion is the mini-
mum erosion rate found for hydrogen erosion of films with
a carbon content of about 15%. Those a-B0.85Cojs:H films
exhibit an erosion rate which is about 40% lower than for
pure a-B:H films. A similar result was observed by Veprek
et al. [5] for the erosion of some BxC films at 630 K and
floating potential in a RF-PECVD H 2 plasma. However,
no such minimum could be observed for helium erosion.
Here we found a monotonous increase of the erosion rate
with carbon content up to x = 0.71. Like for floating
potential at hydrogen erosion, those a-Bo29Co.71:H films
- - the films of lowest film densities (see Fig. 1) - - have a
maximum erosion rate.
But there are some other remarkable differences be-
tween hydrogen (Fig. 2) and helium erosion (Fig. 3). For
hydrogen the difference in the erosion rate between float-
ing potential and 50 V dc self-bias is in general very small;
only for pure a-C:H films a significant difference is found.
For helium, however, the difference between these two
potentials is almost one order of magnitude over the entire
compositional range. We attribute this effect to the fact
that there exists a threshold energy Eth for physical sputter-
ing, which amounts to about 2 5 - 4 0 eV [11,12] for H + and
He + ion bombardment of carbon or boron surfaces. This
threshold energy is higher than the ion energy at floating
153
potential in our experiments. Therefore, we should expect
for floating potential a negligible contribution of physical
"" "--~,.'--,
sputtering to the total erosion rate. This clearly indicates
the dominance of chemical erosion [8,13,14] by atomic
a hydrogen H ° for ion energies of less than about 50 eV,
ingly, there also exists a small, but non-negligible erosion
rate (2.8 p m / s ) of a-B:H films with hydrogen at floating
potential which we attribute to chemical erosion of boron
by atomic hydrogen.
80 100
Erosion at floating potential with helium, which was
found especially for carbon rich films, seems to be impos-
sible at first sight. There can be no chemical erosion by
helium and the threshold energy for physical erosion is
higher than the maximum ion energy of helium at floating
potential. Here we have to take into account plasma impu-
rities (base pressure being about 10 -4 Pa). Dominant parts
of those impurities are H 2 0 and CO x. It is well known that
especially carbon shows chemical erosion by oxygen,
forming volatile CO x molecules [16]. This was one impor-
tant problem for carbonized fusion experiments in the
1980s [2,17]. Since boron has a good getter effect on
oxygen [1,2], forming non-volatile B203 [18], the erosion
of boron rich films by impurities can be neglected.
4. Summary
a-B=_xC ~:H films were deposited over the entire com-
positional range from pure a-B:H ( x = 0) to pure a-C:H
( x = 1) films. The erosion of these films was investigated
in hydrogen and helium ECR plasmas as a function of the
ion energy. The erosion rate depends strongly on film
composition and ion energy. For hydrogen erosion of
a-B i_ ~Cx:H films a minimum erosion rate occurs for films
with a carbon content of 15% at all investigated ion
energies. However, this minimum cannot be found for the
erosion with helium plasmas. This result is important for
future fusion devices as ITER, because the helium ash is
always present in a fusion plasma. From the differences of
the hydrogen and helium erosion we concluded that chemi-
cal erosion of a-B:H films by atomic hydrogen is, as for
carbon films, the dominant erosion mechanism at low ion
energies.
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