ANNEALING CHARACTERISTICS OF nTYPE DOPANTS IN IONIMPLANTED

SILICON
B. L. Crowder and F. F. Morehead Jr.

Citation: Applied Physics Letters 14, 313 (1969); doi: 10.1063/1.1652664

View online: http://dx.doi.org/10.1063/1.1652664
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 Volume 14, Number 10 APPLIED PHYSICS LETTERS 15 May 1969

characterizing the doping characteristics of ion-
implanted silicon as well as other impurities in
gallium arsenide. As an example of these, prelim-
inary results with ion-implanted carbon into semi-
insulating gallium arsenide show it to be an accep-
tor with fairly low doping efficiency.
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8 J. Lindhard, M. Scharff, and H. Schiott, Kgl.

2N. Goldsmith and W. Kern, RCA Rev. 28, 153 Danske Videnskab Mat.-Fys. Medd. Selskab 33
(1967). (1963).
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Soc. 111, 874 (1964). R. Baron, C. J. Phys. 45, 4073 (1967).

ANNEALING CHARACTERISTICS OF n-TYPE DOPANTS IN ION-IMPLANTED

SILICON
B. L. Crowder and F. F. Morehead, Jr.
IBM Watson Research Center
Yorktown Heights, New York 10598
(Received 24 February 1969; in final form 14 April 1969)

Investigations of the conditions under which the donors, P, As, and Sb, are incorporated into Si by
by ion implantation (260-300 keY) in an electrically active form are reported. Above a critical
dose, room-temperature implantations followed by a 600°C post anneal are substantially more ef-
fective than implantations at 600°C.

A major factor in the rapid growth of research
in ion-implantation doping of semiconductors is the
potential of this technique in the fabrication of elec-
tronic devices. The conditions under which a ma-
jority of implanted ions can be obtained in an elec-
trically active form are of considerable importance.
Heavy ions produce clusters of grossly damaged
material in addition to point defects around the
periphery of the gross damage. 1 If the damage is
not annealed during the implantation, a layer of
amorphous Si is formed when the individual dam-
age clusters overlap. The elimination of radiation
damage and the incorporation of the implanted spe-
cies on electrically active sites (generally substi-
tutional positions), uncompensated by defects, are
of primary concern in achieving optimum electrical
activity in the implanted layer.
Previous investigations 2 of the electrical activity
of implanted donor species in Si have implied indi-
rectly that the conditions under which radiation
damage is annealed during the implantation (e.g.,
at implantation temperatures greater than 450°C
in Si at the dose rates usually employed) are to be
preferred to implantations at room temperature
which produce enough damage to create overlap of
damage clusters and the formation of an amorphous
layer.
We wish to report on investigations of Si doped
with the donors P, As, and Sb by ion implantation
in the energy range 260-300 keY. In a previous
study, the total concentration profiles of P and As
in ion-implanted Si were investigated, utilizing
neutron activation and anodic oxidation stripping
techniques. 3 In the present work, we have concen-
trated on the electrical properties (resistivity, Hall
coefficient) of the implanted layers. In many cases
room-temperatul'e implantations followed by a post
anneal at a given temperature (e.g., 600°C) may be
more efficacious in producing electrically active
species than an implantation conducted at that tem-
perature.
The Group V ions were implanted into Si samples
using a Cockcroft-Walton accelerator operating
between 260-300 kV. The ions P and As were ob-
tained from gaseous species (PF s , AsH3) in an os-
cillating electron source of our design. 4 An Ar
plasma was used to heat solid Sb in a quartz cru-
cible suspended inside the same source, thereby
obtaining a sufficient vapor pressure of Sb. The ion
beam was focussed, mass analyzed magnetically,
and scanned uniformly over the sample (4cm2).
The Si substrates were (100) oriented, boron-doped,
and had a resistivity of 1 O-cm. It was possible to
heat the samples as high as 700°C during implanta-
tions. The total dose was obtained by integrating
the current from the samples (room-temperature
implantations) or from a beam profile monitor
(high-temperature implantations). The currents
were measured with a Faraday cup. Dose rates
were typically 1-5 I1A/cm 2.

313

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 Volume 14, Number 10 APPLIED PHYSICS LETTERS 15 May 1969

Table I. Electrical characteristics of donor species ion implanted into silicon.

Donor Energy Total dose Implantation Electrical properties after post anneal"
(keV) cm- 2 temperature None 600°C
(OC) Electrons p's Electrons p's
cm- 2 n/D cm- 2 n/D
Sb 260 3x 10 15 30 3 X 10 15 38
Sb 260 3x 10 15 500 0.7 X 10 15
280
Sb 260 3x 10 15 600 0.4 X 10 15 167
As 280 3x 10 15 30 3X 10 15 29
As 260 2.5 x 10 15 600 0.14 X 10 15
133 0.14 x 10 15 133
P 300 3X 10 15 30 0.9 X 10 15 74
P 300 3X 10 15 600 0.16 X 10 15 175 0.16 x 10 15 175
P 300 6X 1014 30 1X 1014 290
P 300 6X 1014 600 0.7 X 10 14 290 0.7 x 1014 290

"The samples implanted at room temerature were given a post implantation anneal for
30 min under a nitrogen atmosphere. The samples implanted at elevated temperatures
were studied with no post implantation annealing and, in some cases, after a 600°C
post implantation anneal. The data are from Hall and sheet resistivity measurements.

To facilitate good electrical contact to the im-
planted regions, the wafers had prediffused contact
pads (As-doped). Clover-leaf van der Pauw 5 con-
figurations were obtained by etching techniques.
Conventional dc potentiometric techniques were
used to measure resistivities and Hall voltages.
A summary of typical results obtained for room-
temperature implantations followed by a t-h anneal
at 600°C and for implantations conducted at 600°C
is given in Table I for P, As, and Sb implants in Si.
lt is readily apparent that a higher degree of elec-
trical activity is achieved in the former case if the
implanted dose is relatively high. The dependence
of this phenomenon upon total dose was investigated
for As and P implantations conducted at room tem-
perature. Isochronal annealing studies (t-h time
periods) were conducted. Figure 1 shows the re-
sults for P implantations at 280 keY. In this figure,
we are plotting the fraction of the total dose im-
planted which is electrically active as determined
from the sheet Hall coefficient as a function of the

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ANNEALING TEMPERATURE (OC)

Fig. 1. The ratio of electrons/cm 2 (obtained

from sheet Hall coefficients) to implanted Fig. 2. The sheet resistivity of As- implanted
atoms/cm 2 for P implantations into Si as a layers in Si as a function of the isochronal
function of the isochronal annealing temper- annealing temperature. The total number of
ature. The total number of P ions/cm 2 im- implanted As ions/cm 2 is shown for each
planted is indicated for each curve. The im- curve. The energy of the As ions was 280
plantation energy was 280 ke V. The duration keY. The duration of annealing at each tem-
of annealing at each temperature was 30 min. perature was 30 min.

314

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 Volume 14, Number to APPLIED PHYSICS LETTERS
isochronal annealing temperature. 6 Substantially
complete electrical activity of the implanted dose
results from 600 0 e post annealing for doses greater
than 10 15 cm- 2 and less than 3 x 10 13 . This result
agrees with that of Gibson et ai.,7 who did not study
the intermediate doses. It is also consistent with
the more complete data of Vasil'ev et ai. 8 reported
for 50-kV P implants in Si.
The data for As implantations are presented in
a different form in Fig. 2, which is a plot of the
sheet resistivity of the implanted layer as a func-
tion of the isochronal annealing temperature. For
these As implants, a large fraction of the As ions
implanted are electrically active after a 550 e an-
neal for total doses of 3 x 10 14/cm 2 and above (elec-
trons/cm 2:As/cm 2 ~ 1).
Two facts are immediately obvious from these
figures: (1) Above a certain critical dose, a large
fraction of the implanted ions can be made elec-
trically active and uncompensated at a fairly low
post-annealing temperature (e.g., 550 0 e). Below
this critical dose, only a small fraction of the im-
planted ions are electrically active after a 550°C
post anneal. This critical dose is 1 x 10 15/cm 2 for
P implantations (280 keY) and 3 x 1014/cm2 for As
implantations (280 ke V). (2) Below the critical
dose, the higher the dose, the higher the tempera-
ture required to obtain a given fraction (e.g., 0.50)
as electrically active 9 and uncompensated.
In the case of the Group V donors, P, As, and
Sb, at the critical dose and above, a completely
amorphous layer of Si is formed which includes the
implanted ions. 7 The recrystallization of this gross
lattice damage in Si occurs in the region of 500°-
600°C and results in the incorporation of the im-
planted ions on substitutional sites such that they
are electrically active and uncompensated. 7 Although
the damage produced by doses too low to render Si
amorphous anneals at much lower temperatures
and apparently incorporates the ions substitution-
ally, as do the high-temperature implants lO , much
higher annealing temperatures are required to pro-
duce a high fraction of the implanted ions in an un-
compensated and electrically active form. This is
an unexpected result and indicates a complex inter-
action between the damage and the implanted P, As,
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IS May 1969
and Sb ions. The annealing characteristics of the
room-temperature implantations of these ions be-
low the critical dose is also unexpected. There is
evidently much more to be learned about the nature
and location of the damage centers produced in Si
by heavy ion bombardment.
10. J. Mazey, R. S. Nelson, and R. S. Barnes,
Phil. Mag. 17, 1145 (1968).
2J. W. Mayer, O. J. Marsh, G. A. Shifrin, and
R. Baron, Can. J. Phys. 45, 4073 (1967).
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0
published).
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Instr. (to be published).
5 L. J. van der Pauw, Philips Res. Rept. 13, 1
(1958).
2
6 The number of carriers/cm determined from
the sheet Hall coefficient is only an apprOXimate
measure of the total number of carriers which are
electrically active. The sheet Hall coefficient is an
average which weights the carriers of higher mo-
bility more heavily, leading to a smaller value than
the true number of carriers/cm 2. In extreme cases
(Ref. 2), the sheet Hall coefficient may give carrier
concentrations/cm 2 which are only 50% of the true
values. Stripping studies, in progress, indicate that
the discrepancy is usually less than this for our
implantations (70-95%).
7W. M. Gibson, F. W. Martin, R. R. Stensgaard.,
F. Palmgren Jensen, N. I. Meyer, G. Galster, A.
Johansen, and J. S. Olsen, Can. J. Phys. 46, 675
(1968).
8 V. K. Vasil'ev, E. t. Zorin, P. V. PavlOV, and
D. I. Tetel'baum, Fiz. Tverd. Tela 9, 1905 (1967)
[English transl.: Soviet Phys.-Solid State 9, 1503
(1968)].
9 This fact is not so obvious for As implants from
Fig. 2. The ratio of electrons to implanted As does
exhibit the type of dose dependence as shown for P
in Fig. 1.
10 L. Eriksson, J. A. Davies, N. G. E. Johansson,
and J. W. Mayer, J. Appl. Phys. 40, 841 (1969);
R. Baron, G. A. Shifrin, O. J. Marsh, and J. W.
Mayer, J. Appl. Phys. (to be published).
315