Journal of Non-CrystalllneSolids 35 & 36 (1980) 441-446

~North-Holland Publishing Company

OPTICAL PROPERTIES OF LPCVD aB(H)

B. G. Bagley, D. E. Aspnes, +
A. C. Adams and R E. Benenson-

Bell Laboratories
Murray Hill, New Jersey
U.S.A.

Amorphous boron-hydrogen alloys (9 to 24 at % H) have been

prepared and optical properties determined. In the ir,
the only bands observed involving H are the B-H stretch
at 2560 cm -I and the B-H bend at 1108 cm-l; no evidence
is found for bands associated with BH 2 groupings or H
three-center bonds. In the visible-near uv, the e2 spec-
trum for the sample with 9 at % H has a broad maximum near
5eV with a peak value of 6. With increasing H content,
both optical gap and c 2 peak move to higher energies,
while the c 2 peak value and refractive index decrease.

INTRODUCTION

As an elemental semiconductor, the properties of amorphous boron (aB)

have been of interest (see, for example, the review by Moorjani and
Feldman [1]). The introduction cf hydrogen into amorphous boron can
have a marked effect on properties, analogous to that observed in
amorphous silicon and amorphous germanium. For example, the optical
properties of hydrogen-containing amorphous boron films prepared by
plasma deposition have been recently reported [2,3,4] and they are
indeed different from those of the unhydrogenated material.

In a recent study of the preparation and properties of boron nitride

films, Adams and Capio [5] have shown that hydrogen-containing amor-
phous boron films can be prepared by the technologically important
low pressure chemical vapor deposition (LPCVD) technique. The im-
portance of LPCVD arises from its potentially high production capa-
bility and chemical reaction controllability. We have prepared a
series of amorphous boron-hydrogen, aB(H), alloys with varying hydro-
gen content by LPCVD and determined their optical properties, and
report our results here.

EXPERIMENTAL

The samples were prepared by low pressure chemical vapor d e p o s i t i o n

using the pyrolysis of diborane (15% in argon) at 0.5 torr. The de-
position reactor and deposition conditions are described in detail
elsewhere [5]. The hydrogen content in the films is determined by
the reaction temperature. ReactiOn temperatures for the samples

tResident Visitor. Permanent Address: Department of Physics, State

University of New York at Albany, Albany, New York 12222 U.S.A.

441
442 8.G. Bagley et al. / Optical Properties of LPCVD aB(H)

studied here were 290, 340, and 400C. The films were deposited onto
7.5 cm diameter polished single crystal silicon substra~es. The
deposition rate increased from 44 A/min at 290C to 400 A/min at 400C.
Film thicknesses ranged from .34 to 1.4 ~m. Samples prepared at
400C were highly stressed, and at thicknesses exceeding ~ .7 ~m
would begin to separate from the substrate.

The hydrogen c~ntent a n d ! i s depth profile were determined for each

sample by the H(15N,ey)IZC (4.43 MeV) resonant nuclear reaction [6].
A 15N++ beam was incident normally on the aB(H) sample mounted in
the end cap of the beam line. The 4.43 MeV gamma ray, which repre-
sents the H signal, was detected by a 12.5 cm diameter by 12.5 cm
long NaI scintillator at zero degrees with respect to the 15N beam.
The ~ concentrations were obtained by measuring sample counting
rates relative to fresh polyethylene (CH2) n under the same beam con-
ditions. The H to B atomic ratio (NH/NB) can then be calculated
using tabulated atomic stopping cross sections for nitrogen. For B
the Northcliffe and Schilling Tables [7] were used, and for C and H
values recently revised by Zieglt !8]. The estimated uncertainty
in NH/N B is 12 percent due to variations in the calibration standard
(this observed variation may have a contribution due to other com-
ponents in the 15N ++ beam) and an uncertainty in the values of the
stopping cross sections. Additional details are published else-
where [9].

I n f r a r e d d a t a were taken with a Perkin Elmer model 580 Spectrometer

with a matching silicon wafer in the reference beam. Dielectric
function spectra E = e I + ie 2 were taken from 1.5-5.8eV with a
rotating-analyzer ellipsometer described in detail elsewhere [10,11].
The raw tan ~, cos ~ data were reduced by means of the standard two-
phase model to yield the dielectric function. The sample surfaces
were rinsed with methanol prior to measurement, and all data were
taken with samples held in a dry N2 ambient in a windowless cell to
minimize contamination.

RESULTS AND DISCUSSION

The hydrogen content of the resulting films, as a function of deposi-

tion temperature, is as follows:

Deposition Temperature NH/N B NH/(NH+N B)

290C .32 .24
340C .12 .11
400C .10 .09

The results of the hydrogen profiling indicated that all the samples
were homogeneous in hydrogen content.

In addition to skeletal modes found at low energies, only two peaks

involving hydrogen were observed in the ir transmission spectra; a
B-H stretching mode at 2560 cm -I and a B-H bending mode at 1108 cm -I.
The intensities vary with hydrogen content but the frequencies do
not. Other bands, as might be associated with BH 2 groupings or hy-
drogen three-center bonds, were not detected. These results are the
same as that observed previously by Bagley et al. [4] for plasma
deposited aB(H). They differ, however, from the observations
reported by Berezin et al. [12] and Tsai [3] on their samples.
Whereas in all these studies the 2560 cm-i band is observed, Berezin
et al. [12] and Tsai [3] also observe a strong, very broad band near
 8.G. Sagleg et alo / Optical Properties of LPCVD aB(H) 443

1900-2000 cm -I which Tsai attributes to a hydrogen three-center

bridge bond and which we do not observe. Because the resulting
material depends intimately on deposition conditions, it is likely
that differences reflect an actual material disparity.

The optical properties (~1 + ie2) in the visible and near uv (1.5-
5.8eV) for samples deposited at the three reaction temperatures are
shown in Figure i. Data are shown to as low an energy as the onset
of the interference fringes caused by reflection from the substrate.
The aB(H) with 9 at % H(400C deposition) has an c 2 spectra which
shows a broad maximum near 5eV with a peak value-of about 6. The
peak~value drops with increasing hydrogen content. At 24 at % H
(290C deposition) th~ ~2 peak energy has moved above 5.SeV, the l i m i t
of our ellipsometer. The long wavelength refractive index decreases
with increasing hydrogen content due both to a decrease in oscilla-
tor strength and to a shift of the oscillator strength to higher
energy.

t0 I i I i I l I i
OB(H)
400C
- - - --- 340 C

------ 2goc

/
I
I
6
N
w
m,
qp,.

.,4"
j w

e
~

I
2
i I
3
i

E (ev)
I
4
~ I
5
i
Figure 1
The real and imaginary parts, ~1 and ~2, of the
dielectric function vs, energy for samples deposited
at the three reaction temperatures. The low energy
structure on each curve is due to the onset of back
reflection from the substrate.

In Figure ~ are shown the ~2 data plotted as rE2% vs. E (energy).

If the energy bands are parabolic but the momentum is not conserved
in t~e optical excitation process, then ~his ~lot will be a straight
line near the absorption edge for ~ > i0 cm- . The intercept of
~ B.C-, 8agley et al. / Optical Properties of LPCVD aS(H)

OB(H)
t2 400C
..... 340(::
.... 290C
>
8

bJ

//
or_ 2 3
E (eV)
4 5
t
Figure 2
A plot of the square root of e 2 times energy (E)
vs. energyl The intercept of the low energy linear
portion of the curve defines the optical gap E 0.

2.2

t.e

>
1.4
o
u.I

1.0

~) 0.t 0.2 0.3

N H / ( N H + N B)

Figure 3
The optical gap, E0, as a function of the atomic
fraction of hydrogen. The datum at 0 is for evapo-
rated aB and is taken from reference [1]. The
datum at ..29 is for plasma deposited aB(H) and is
taken from reference [4].
 B.G. Bagley et al. / Optical Properties of LPCVD aB(H} 4~5

this plot defines an optical gap, E 0 [13,14]. W e observe that

E 0 = 1.10 ± 0.05eV, 1.15 ± 0.05eV, and 1.7 ± 0.1eV for the samples
containing 9 at %, ii at %, and 24 at % H, respectively. Over the
composition range 0 to 29 at % H the optical gap appears to be a
linear function of the hydrogen content as is shown in Figure 3.
The datum at 0 % H is for evaporated aB and is taken from reference
[1], and the datum at 29 at % H is for plasma deposited aB(H)~and is
taken from reference [4].

The films appear chemically stable. Upon exposure to a laboratory

ambient for 6 months there is no detectable change in the optical
properties of the films. Rescans in the ir region repeated the
earlier spectra and there was no detectable O-H or B-O bands as
usually occurs in the degradation of B-H materials. E11ipsometric
rescans indicated the presence of a thin surface layer which was
removable with methanol, whereupon the earlier results were dupli-
cated. These data showed only that the surface layer.was trans-
parent, and could not distinguish between a natural oxide or
hydrocarbon contamination.

REFERENCES
[i] Moorjani, K. and Feldman, C., in:Matkovich, V. I. (ed.), Boron
and Refractory Borides (Springer-Verlag, Berlin, 1977) p. 581.

[2] Tsai, C. C., Fritzsche, H., Tanielian, M. H., Gaczi, P. J.,

Persans, P. D. and Vesaghi, M. A., in: Spear, W. E. (ed.),
Proceedings of the Seventh International Conference on
Amorphous and Liquid Semiconductors (Center for Industrial
Consultancy and Liason, University of Edinburgh, 1977) p. 339.

[3] Tsai, C. C., Phys. Rev. B 19 (1979) 2041.

[4] Bagley, B. G., Aspnes, D. E., Benenson, R. E., Adams, A. C.,

Alexander, F. B. and Mogab, C. J., Bulletin Amer. Phys. Soc. 24
(1979) 399 and to be published.

[5] Adams, A. C. and Capio, C. D., J. Electrochem. Soc., in press.

[6] Lanford, W. A., Nucl. Instr. and Meth. 149 (1978.) i.

[7] Northcliffe, L. C. and Schilling, R. F.~ Nuclear Data Tables A7

(1974) 463.

[8] Ziegler, J. F., Stopping Powers and Ranges, Vol. 5, to be

published; communicated by W. A. Lanford.

[9] Benenson, R. E., Feldman, L. C. and Bagley, B. G., Nucl. Instr.

and Meth., in press.

[i0] Aspnes, D. E. and Studna, A. A., Appl. Opt. 14 (1975) 220.

[ii] Aspnes, D. E. and Studna, A. A., Rev. Sci. Instrum. 49 (1978)

291.
446 B.G. Bagley et al. / Optical Properties of LPCVD aB(H)

[12] Berezin, A. A., Golikova, O. A., Kazanin, M. M., Khomidov, T.,

Mirlin, D. N., Petrov, A. V., Umarov, A. S. and Zaitsev, V. E.,
J. Non-Crystalline Solids 16 (1974) 237.

i13] Tauc, J., Abraham, A., Pajosov~, L., Grigorovici, R. and

Vancu, A., in: Prins, J~ A. (ed.), Physics of Non-Crystalline
Solids (North Holland, Amsterdam, 1965) p. 606.

[14] Mott, N. F. and Davis, E. A., Electronic Processes in

Non-Crystalline Materials (Clarendon Press, Oxford, 197~)
p. 248.