Chemical erosion of amorphous

hydrogenated boron films

Cite as: Appl. Phys. Lett. 71, 1326 (1997); https://doi.org/10.1063/1.119885
Submitted: 28 April 1997 • Accepted: 07 July 1997 • Published Online: 04 June 1998

A. Annen and W. Jacob

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Appl. Phys. Lett. 71, 1326 (1997); https://doi.org/10.1063/1.119885 71, 1326

© 1997 American Institute of Physics.

Chemical erosion of amorphous hydrogenated boron films
A. Annen and W. Jacoba)
Max-Planck-Institut für Plasmaphysik, EURATOM Association, D-85748 Garching, Germany
~Received 28 April 1997; accepted for publication 7 July 1997!
Amorphous-hydrogenated boron ~a-B:H! and carbon ~a-C:H! thin films were prepared by
radio-frequency plasma deposition using (B2H61H2) or CH4 as a precursor gas. The film
composition and density were investigated by ion-beam analysis. The films were eroded by
hydrogen electron cyclotron resonance plasmas at floating potential and by atomic hydrogen
dissociated by a hot filament. The temperature of the substrates was increased during the erosion
process from 330 to 680 K. Erosion rates were measured in situ by ellipsometry. a-B:H films are
shown to be much more resistant to erosion by hydrogen ions (H1) and atomic hydrogen (H0) than
a-C:H films. In contrast to a-C:H films, no chemical erosion of a-B:H films by H0 was observed at
temperatures below 600 K. Ion energies lower than the threshold energy for physical sputtering
cause measurable erosion rates for a-B:H films. It is concluded that this is a synergistic effect of
simultaneous H0 and H1 bombardment and it is designated as ion-induced chemical erosion.
© 1997 American Institute of Physics. @S0003-6951~97!02636-3#

Erosion of solid surfaces due to light-ion and neutral
bombardment is of great importance in fusion experiments.1
The inner walls of most fusion experiments are covered with
thin, amorphous hydrogenated boron films by plasma depo-
sition. Furthermore, larger components ~divertor and limit-
ers! consist of carbon, owing to the excellent thermome-
chanical properties of this element. The erosion of boron and
carbon films is, therefore, the object of our investigations. In
a previous publication, we reported the erosion of amorphous
hydrogenated boron/carbon (a-B12x Cx :H) films by hydro-
gen and helium as a function of the ion energy.2 It was
shown that the erosion rate strongly depends on the film
composition and ion energy. Pure a-B:H films exhibit sig-
nificantly lower erosion rates in H2 and He plasmas than pure
a-C:H films. We also observed erosion of a-B:H films at
hydrogen ion energies well below the threshold energy of
physical sputtering. This suggests that chemical erosion of
boron films by thermal, atomic hydrogen, as with carbon
films,3,4 is the dominant erosion mechanism at low ion ener-
gies. In this study, this question is clarified by eroding pure
a-B:H and a-C:H films with atomic hydrogen and, for com-
parison, in hydrogen plasmas at floating potential as a func-
tion of the film temperature.
Amorphous hydrogenated boron ~a-B:H! and carbon
~a-C:H! thin films were prepared by capacitively coupled
13.56 MHz radio-frequency plasma deposition using
(B2H61H2) or CH4 as a precursor gas. The detailed descrip-
tion of the deposition apparatus is given elsewhere.5 The
complete set of deposition parameters is shown in Table I.
As a substrate material, we used p-type single-crystalline
silicon. The film growth was controlled in situ by means of a
He–Ne laser interferometer. After deposition, the film thick-
ness d s was determined ex situ with a Tencor Alpha Step 200
profilometer. Together with d s , the index of refraction n can
be calculated from the interference pattern. The film compo-
sition and atom densities were measured by ion-beam
analysis.5 The hydrogen content was determined by 2.6 MeV
a!
Corresponding author. Electronic mail: jacob@ipp.mpg.de
He1 elastic recoil detection, the boron content by 2.6 MeV
11
B(p, a ) 8 Be nuclear reaction analysis and the carbon con-
tent by 1.5 MeV H1 proton-enhanced cross-section scatter-
ing. Films were eroded by hydrogen electron cyclotron reso-
nance ~ECR! plasmas at the floating potential and by thermal
atomic hydrogen (H0) thermally dissociated from H2 by a
tungsten filament. The erosion rates were determined in situ
by ellipsometry. For a detailed description of the plasma re-
actor, plasma parameters, and ellipsometric setup, see Refs.
2, 4, and 6. The base pressure of the plasma reactor is about
1024 Pa. To allow comparison of the erosion rates for the
various samples, the plasma parameters were kept constant.
The gas flow for the H2 plasma was 20 sccm, the gas pres-
sure 0.5 Pa, and the absorbed microwave power density
0.01 W/cm3. The ion energy at floating potential is estimated
to be below 15 eV. For the thermal dissociation of H2, the
gas flow was 30 sccm, the gas pressure was 10 Pa, and the
tungsten filament ~1.1 V! was heated with 11 A, yielding a
temperature of 2200 K as measured by pyrometry. Some
samples were analyzed ex situ by x-ray photoelectron spec-
troscopy after a hydrogen treatment to check for a possible
tungsten deposition on the specimen surface. On none of the
samples investigated was a measurable tungsten deposition
found. The temperature of the electrode, which can be varied
by resistive heating, is measured by a thermocouple in the
substrate holder. To obtain a good thermal contact between
the samples and the electrode, colloidal carbon was used as a
bonding substance.4
The properties of the deposited a-B:H and a-C:H films
TABLE I. Parameters of deposited a-B:H and a-C:H films.
Parameter Value
Precursor gases B2H6 ~10%! in H2, CH4
Rf frequency 13.56 MHz
Gas flow 10 sccm
Gas pressure 2 Pa
Rf power density 0.65 W/cm2
Dc self-bias 235 V
Substrate temperature 330 K

1326 Appl. Phys. Lett. 71 (10), 8 September 1997 0003-6951/97/71(10)/1326/3/$10.00 © 1997 American Institute of Physics
TABLE II. Properties of the eroded a-B:H and a-C:H films.
Hydrogen
Film Boron/carbon atom Mass
thickness Refractive atom density density n H density
d s ~nm! index n n B /n C (1022 cm23) (1022 cm23) r (g/cm3)
a-B:H 125 2.55 9.4 3.3 1.74
a-C:H 150 2.09 8.3 3.5 1.72
are shown in Table II. The refractive index, atom density,
and hydrogen content of the films are typical of dense,
chemically, and mechanically stable a-B:H ~Ref. 7! and hard
and dense a-C:H films,8 respectively, since the films were
prepared at relatively high ion energies ~see Table I!. Amor-
phous hydrogenated boron films have higher atom densities
and refractive indexes, but lower hydrogen content and
nearly the same mass density as amorphous hydrogenated
carbon films deposited at the same deposition parameters ~cf.
Refs. 7 and 9!.
The a-B:H and a-C:H films were eroded in hydrogen
ECR plasmas and with atomic hydrogen. During the erosion
process, the film temperature T f was increased from about
320 to 680 K. The ellipsometrically measured erosion rates
are summarized in Fig. 1. It has to be mentioned that the
erosion rates of films in hydrogen plasmas and with atomic
hydrogen H0 are not directly comparable, because the fluxes
of hydrogen ions H1 and neutrals H0 onto the films are not
known. Only the erosion rates of a-B:H and a-C:H in hydro-
gen plasmas and with H0, respectively, and the temperature
dependence of the films are directly comparable. Obviously,
the erosion rates of a-C:H films in hydrogen plasmas at
floating potential and during exposure to H0 are significantly
larger than those of a-B:H films. The difference is between
one and two orders of magnitude in the observed temperature
region.
For a-C:H, we find a more or less exponential increase
FIG. 1. Erosion rates of a-B:H ~squares! and a-C:H ~circles! films eroded
by hydrogen plasmas ~blank symbols! and by atomic hydrogen ~solid sym-
bols! as a function of the film temperature. The dashed lines are only a guide
to the eye. The dotted line represents the erosion rate of a-C:H by H0
multiplied by a factor of 6.5.
Appl. Phys. Lett., Vol. 71, No. 10, 8 September 1997
of the erosion rate by H0 between 400 and 600 K in accor-
dance with earlier results.4 For T f above 575 K, the rate
saturates and a maximum is indicated at 670 K. The erosion
of a-C:H in hydrogen plasmas at floating potential shows the
identical temperature dependence for T f above 475 K. The
only difference is that the rate is increased by a factor of 6.5.
This is demonstrated by the dotted line in Fig. 1, which
shows the data for H0 etching multiplied by 6.5. For T f be-
low 475 K, the rate in the plasmas shows a much weaker
temperature dependence than for H0. Erosion of a-B:H films
in hydrogen plasmas results in rates, which at low T f , are a
factor of 20 lower than for a-C:H. The increase with T f
between 350 and 475 K is similar to that of a-C:H, but at
high T f it is much weaker. While the rate for a-C:H in-
creases by a factor of 7 between 450 and 575 K, it only
increases by a factor of 3 for a-B:H. At 575 K, a-B:H ex-
hibits the maximum erosion rate followed by a significant
decrease at higher T f . In contrast to a-C:H, we measure no
erosion of a-B:H due to H0 for T f below 600 K. Only for
T f >600 K we do obtain erosion rates, which are above, al-
beit only slightly, the detection limit of our ellipsometric
measurement of about 0.1 pm/s, corresponding to 1 ML per
30 min.
The energy of the hydrogen ions in our hydrogen ECR
plasma at floating potential is estimated to be less than 15
eV. The threshold energy E th for physical sputtering may be
calculated empirically10,11 as E th5 @ 7 * (M 2 /M 1 ) 20.54
10.15* (M 2 /M 1 ) 1.12# * E s , with the sublimation energy E S
57.4 eV for graphite and 5.8 eV for boron,11 M 1 being the
projectile mass ~hydrogen! and M 2 the target mass ~carbon
or boron!. From this, we calculated E th for the sputtering of
B or C from a-B:H and a-C:H to be about 24 and 32 eV,
respectively. Obviously, the H1 energies at the floating po-
tential are well below these threshold energies, so that no
physical sputtering is possible. Nevertheless, Fig. 1 demon-
strates that erosion of a-C:H and ~less, but not negligible!
a-B:H films occurs in plasmas of such low ion energies. For
graphite and hydrocarbon ~a-C:H! films, this effect is well
known as chemical erosion, caused by thermal atomic hydro-
gen H0 and hydrogen ions H1 of low energy.3,4,12 An energy
and temperature-dependent erosion rate with a maximum at
600–700 K for H0 ~Ref. 3! and 800 K for H1 ~Ref. 12! was
observed. CH3 radicals are eroded via thermally activated
chemical reactions of H0 with C:H,13 and also radicals of
higher hydrocarbons Cx Hy , especially C2Hy , have been
measured.3 Furthermore, synergistic effects between H0 and
H1 are known for the erosion of carbonaceous materials.14,15
Our measurements for the erosion of a-C:H are in good
agreement with these published results. We find a strong
increase of the erosion rates with temperature, with a maxi-
mum for H0 at about 670 K. Unfortunately, we are not able
to measure the flux of hydrogen ions and neutrals, so that the
absolute erosion yields of H0 and H1 with a-C:H cannot be
calculated.
Unlike carbon, chemical erosion of boron with atomic
hydrogen has not hitherto been proved. On the contrary, bo-
ron is known to reduce the chemical erosion of a-C:H
films.10,16,17 Only Winter et al.18 proposed chemical erosion
of boron by means of volatile BH2 or BH3. In a previous
publication,2 we reported small, but not negligible erosion of
A. Annen and W. Jacob 1327
an a-B:H film by a hydrogen plasma even at floating poten-
tial and T f 5330 K, which is not much lower than erosion
with ion energies of up to 50 eV. This observation was
clearly different from the erosion in a helium plasma, where
only negligible erosion was observed at floating potential,
whereas there was a relatively high erosion rate at 50 eV. In
this work, it is shown that there is a temperature-dependent
erosion rate for a-B:H films in hydrogen plasmas with low
ion energies, too. The maximum is found to be at lower T f
~575 K! than for a-C:H films, and the rates are still lower by
more than one order of magnitude. The erosion of a-B:H
with thermal H0 is negligible and below our detection limit
for T f ,600 K. So, the direct contribution of this H0, or
chemical erosion in the original sense, is negligible for the
erosion of boron in hydrogen plasmas. It is supposed that a
synergistic effect between thermal H0 and H1 of low ener-
gies ~down to a few eV! causes the observed erosion of
a-B:H in hydrogen plasmas at floating potential. We will
designate this effect as ion-assisted chemical erosion.
Not only a-C:H, but also a-B:H films, are eroded in H2
plasmas with ion energies lower than the threshold energy
E th for physical sputtering. Previous results for the chemical
erosion of carbon with H0 and H1 are confirmed. The ero-
sion of a-B:H films in H2 plasmas exhibits a temperature
dependence similar to that of a-C:H films, but at distinctly
lower rates and a lower temperature maximum ~575 K!. Un-
like a-C:H films, the chemical erosion of a-B:H with H0 is
negligible for temperatures lower than 600 K. Erosion of
a-B:H films in H2 plasmas is supposed to be a synergistic
1328 Appl. Phys. Lett., Vol. 71, No. 10, 8 September 1997
effect between thermal H0 and low-energy H1. It is, in this
sense, not a true chemical erosion process where the desorp-
tion energy is provided by thermal energy, but it may be
called chemically enhanced physical sputtering or, as we
would prefer, ion-assisted chemical erosion.
1
J. Winter, Plasma Phys. Controlled Fusion 38, 1503 ~1996!.
2
A. Annen, A. von Keudell, and W. Jacob, J. Nucl. Mater. 231, 151 ~1996!.
3
E. Vietzke and V. Philipps, Fusion Technol. 15, 108 ~1989!.
4
A. von Keudell and W. Jacob, J. Appl. Phys. 79, 1092 ~1996!.
5
A. Annen, R. Beckmann, and W. Jacob, J. Non-Cryst. Solids 209, 240
~1997!.
6
W. Fukarek and A. von Keudell, Rev. Sci. Instrum. 66, 3545 ~1995!.
7
A. Annen, M. SaX, R. Beckmann, and W. Jacob, Thin Solid Films ~in
press!.
8
Y. Catherine, Mater. Sci. Forum 52&53, 175 ~1989!.
9
A. von Keudell, A. Annen, and V. Dose, Thin Solid Films ~to be pub-
lished!.
10
C. Garcia-Rosales, J. Nucl. Mater. 211, 202 ~1994!.
11
W. Eckstein, C. Garcia-Rosales, J. Roth, and W. Ottenberger, Sputtering
data, Technical Report No. IPP 9/82, Max-Planck-Institut für Plasma-
physik, Germany, 1993.
12
C. Garcia-Rosales and J. Roth, J. Nucl. Mater. 196-198, 573 ~1992!.
13
M. Wittmann and J. Küppers, J. Nucl. Mater. 227, 186 ~1996!.
14
A. A. Haasz, J. W. Davis, O. Auciello, P. C. Stangeby, E. Vietzke, K.
Flaskamp, and V. Philipps, J. Nucl. Mater. 145-147, 412 ~1987!.
15
J. W. Davis, A. A. Haasz, and P. C. Stangeby, J. Nucl. Mater. 155-157,
234 ~1988!.
16
J. W. Davis and A. A. Haasz, J. Nucl. Mater. 195, 166 ~1992!.
17
A. Schenk, B. Winter, C. Lutterloh, J. Biener, U. A. Schubert, and J.
Küppers, J. Nucl. Mater. 220-222, 767 ~1995!.
18
J. Winter, H. G. Esser, L. Könen, V. Philipps, H. Reimer, J. v. Seggern, J.
Schlüter, E. Vietzke, F. Waelbroeck, P. Wienhold, T. Banno, D. Ringer,
and V. Veprek, J. Nucl. Mater. 162-164, 713 ~1989!.
A. Annen and W. Jacob