Solid Solubility and Diffusion Coefficients of

Boron in Silicon
G. L. Vick and K. M. Whittle
Instrument~Controls Division, Conrac Corporation, Duarte, California

ABSTRACT
The solid solubility and diffusion coefficients of boron in silicon have been
determined as a function of t e m p e r a t u r e over the range of 700~176 by
anodically sectioning diffused layers. The solid solubility was found to v a r y
from 1.6 x 1019 a t o m s / c m 3 at 700~ to 2.4 x 1020 a t o m s / c m ~ at 1151~ The
diffusion coefficients for i m p u r i t y levels below l0 TM a t o m s / c m 3 m a y be r e p r e -
sented by D = 6.0 x 10 -T exp (--38600/RT). The diffusion coefficients above
10TM a t o m s / c m 3 were found to be d e p e n d e n t on the i m p u r i t y level.

I n view of the importance of boron as a dopant in formed to d e t e r m i n e w h e t h e r there was precipitation

the technology of silicon electronic devices, there is
a r e m a r k a b l e paucity of i n f o r m a t i o n regarding the
solid solubility of boron in silicon. I n T r u m b o r e ' s re-
view of solid solubilities of elements in g e r m a n i u m
and silicon (1), boron is represented b y only two
points, a eutectic point and a single point based on
diffusion data.
This paper describes a series of experiments in
which boron is diffused into silicon at a n u m b e r of
different t e m p e r a t u r e s b e t w e e n 700 ~ and 1151~ from
an effectively infinite source. The resulting diffusion
profiles are anodically sectioned to determine the solid
solubility of boron in silicon as a function of t e m p e r a -
ture. The diffusion coefficients of boron in silicon are
also calculated as a function of t e m p e r a t u r e and boron
concentration.
Experimental Procedure
A boron rich glass (B203) is pyrolytically deposited
on the surface of 3.0 to 6.5 o h m - c m n - t y p e wafers at
relatively low t e m p e r a t u r e (688~ The wafers are
t h e n diffused at higher t e m p e r a t u r e s in an nonoxidiz-
ing atmosphere (Nf). U n d e r these conditions the boron
glass is reduced by the silicon, m a k i n g elemental boron
available for diffusion into the silicon. The deposition
and diffusion systems have previously been described
by Whittle and Vick (2). The reduction of the B20~
makes boron atoms available at a rate greater than
the rate at which they are diffused away into the
silicon. This results in a t h i n layer of a b o r o n - r i c h
phase such as that discussed b y Busen et al. (3). This
boron rich phase will act as an effectively infinite
source of boron for diffusion into the silicon. Similar
phases m a y be observed in phosphorus diffusion and
have been used by Kooi (4) in d e t e r m i n i n g solubility
of phosphorus in silicon.
Experiments have been performed which show that
the surface concentrations are i n d e p e n d e n t of all
deposition parameters over a wide range [ref. (2)]
and are i n d e p e n d e n t of diffusion time for all the differ-
ent values of diffusion time reported in this paper
and are dependent only on diffusion temperature. The
work of Owen and Schmidt (5) could be i n t e r p r e t e d
as predicting a surface concentration i n d e p e n d e n t of
time u n d e r certain conditions. This work is not directly
applicable here, however, because the rate of chemi-
cal decomposition of the B20~ controls the rate at
which boron is made available for diffusion. This is
demonstrated b y the fact that the doping will be i n -
hibited by the presence of oxygen in the atmosphere.
The presence of the b o r o n - r i c h phase ensures an ade-
quate supply of boron so that surface concentration
will be d e t e r m i n e d b y the solid solubility.
In view of the departures from c o m p l e m e n t a r y
error function form of the profiles obtained at the
higher t e m p e r a t u r e diffusions, experiments were per-
K e y w o r d s : Solid solubility, diffusion aoefflcient, b o r o n , silicon.
of the boron such as that found for phosphorus by
T a n n e n b a u m (6). Diffused wafers were cooled from
1150~ to room t e m p e r a t u r e in times r a n g i n g from 1
rain to 1 hr w i t h o u t preceptible change i n profile,
leading to the conclusion that precipitation was not
occurring to a n y m e a s u r a b l e amount.
Sectioning of the diffused i m p u r i t y profiles was ac-
complished by anodically growing and then r e m o v i n g
layers of silicon dioxide. Anodic oxide growth was
carried out in a solution consisting of 3 parts e t h y l e n e
glycol and 1 part phosphoric acid at 100V. The oxide
was removed with HF and the anodization repeated.
After e v e r y fifth a n o d i z a t i o n - H F cycle a m e a s u r e m e n t
was made of sheet resistivity and depth of silicon re-
moval. Sheet resistivity was m e a s u r e d by a standard
4-point probe method. Silicon removal was measured
by m a s k i n g off a region of the wafer d u r i n g anodiza-
t i o n - H F cycles a n d m e a s u r i n g the height of the r e s u l t -
ing plateau by means of interference fringes. I r w i n ' s
(7) plot of resistivity vs. i m p u r i t y concentration was
used to determine the i m p u r i t y concentration of suc-
cessively removed layers of boron concentration.
Accuracy
The diffusion t e m p e r a t u r e s were controlled to _ 2 ~
and diffusion times were controlled to --+0.05 rain.
The 4-point probe m e a s u r e m e n t s on a given sample
were consistent from r e a d i n g to reading w i t h i n 1%.
The depth of silicon r e m o v a l was d e t e r m i n e d b y
calibrating the silicon removal per anodization cycle
against depth m e a s u r e m e n t s made by means of i n t e r -
ference fringes. The calibration was made to a depth
of 4~ with an accuracy of _--_~/4 fringe, giving a possible
consistent error of about 7%. I n addition, the r a n d o m
errors, represented as deviations of data points from
the calibration curve a m o u n t e d to about --+5% rms.
The plots of i m p u r i t y concentration vs. depth shown
in Fig. 1 and 2 involve the first derivative of the curve
of conductivity vs. depth which was e x p e r i m e n t a l l y
determined. The deviation of data points from comple-
m e n t a r y error functions in Fig. 1 a n d from the best
smooth curves in Fig. 2 are -+ 13 % rms.
A significant source of inaccuracy in the values of
diffusion coefficient at t e m p e r a t u r e s above 1000~ lay
in graphical integration and differentiation of the i m -
p u r i t y profiles. These procedures are somewhat sub-
jective in n a t u r e and it was found that variations in
diffusion coefficient as large as -+100% could be
achieved b y differing estimations of the slopes. The
values reported in Fig. 4 represent the best j u d g m e n t
of the authors as to the i n t e r p r e t a t i o n of existing data.
At t e m p e r a t u r e s less t h a n 1000~ the diffusions are
too shallow to justify accuracy greater t h a n -+100%.
Solid Solubility
I n Fig. 1 a n d 2 are plotted the curves of i m p u r i t y
vs. depth. The curves for diffusions below 1018~ are

1142

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 V o l . 116, N o . 8 SOLUBILITY AND COEFFICIENTS OF BORON 1143
I I I I I I ~ r i i i
The solid solubility data indicate a lower solubility
of boron in silicon t h a n had previously been reported.
There is, however, little actual data to support a higher
value of solubility. Diffusion profiles having larger sur-
face concentrations have been reported. These, how-
ever, have been calculated on the assumption of a
pxio~ c o m p l e m e n t a r y error function distribution which is
shown to be false for t e m p e r a t u r e s above 1000~
Diffusion Coefficients
For those diffusion profiles which m a y be r e p r e -
sented by the familiar c o m p l e m e n t a r y error function,
I X 1019 ~ , , . ~I Cx = Cserfc ( x / 2 ( D t ) ' / 2 ) , calculation of diffusion co-
efficients is s t r a i g h t f o r w a r d since C~ is the c o n c e n t r a -
o tion of the diffusant at distance x after time t and C~
is the extrapolated surface concentration. All the nec-
essary data can be obtained from the diffusion profiles
i 42 HRS AT 700~
i n Fig. 1.
I X IO ts I I J The profiles which do not fit a c o m p l e m e n t a r y error
0 O-I 0,2 O,S function must be dealt with differently. The possi-
DEPTH FROM SURFACE, MICRONS bilities of source depletion or of i m p u r i t y precipitation
as explanations for the shape of these curves have
Fig. 1. Boron concentration vs. depth from surface been ruled out as described earlier. It m a y be assumed,
then, that the profiles result from a concentration
I XI021 I I I I dependent diffusion coefficient similar to that found
by T a n n e n b a u m (6) for phosphorus. The diffusion
coefficients m a y be calculated as a function of i m p u r i t y
concentration b y a method presented by C r a n k (8)
using the equation
, o o
1 d x ~oCl
I X IO 20
Dc=cl = ~ ~ xdC
2t dc
w h e r e D is the diffusion coefficient at a c o n c e n t r a t i o n
03
C, and x and t are depth and time, respectively.
o~ A p p l y i n g this equation to the curves in Fig. 2 results
AT 1151~ in the dependence of diffusion coefficient on i m p u r i t y
o= IXIO 19 concentration shown in Fig. 4. The slope d x / d c and the
oc
a r e a f : l XdC were determined graphically so that the
o= curves in Fig. 4 should be considered to show a q u a l -
itative t r e n d only. A n accurate d e t e r m i n a t i o n of dif-
o
fusion coefficient as a function of i m p u r i t y concentra-
tion could be made by subjecting the i m p u r i t y profile
IXlO J8 data to computation by a computer. These curves in
Fig. 4 are seen to approach a m i n i m u m value of the
diffusion coefficient at each t e m p e r a t u r e at which the
diffusion coefficient is i n d e p e n d e n t of i m p u r i t y con-
centration.
A plot of the logarithm of the diffusion coefficient vs.
IXlO 17 I inverse t e m p e r a t u r e should yield a straight line since
0 1.0 2.0 3.0 4.0 5.0 6.0 the t e m p e r a t u r e dependence of the diffusion coefficient
DEPTH FROM SURFACE , MICRONS follows the form
Fig. 2. Boron concentration vs. depth from surface D = Do exp ( E J R T )
where Ea is the activation energy for diffusion, R is
found to fit well the c o m p l e m e n t a r y error function. the gas constant, and T is the absolute temperature.
For diffusion at 1018~ and higher the curves are sim-
ply the smooth curve which best fits the data. Solid
solubilities are obtained b y extrapolating the diffusion Ic~IO I IIIIIII I I1[11111 I IIIIIHI I lllllll:
profiles to zero depth and are plotted vs. t e m p e r a t u r e
in Fig. 3. /

~lXlO ~ I I I I f

Ij
~ J~7~2
E
1
~ IXIO 20 o

w "I j I / ~
~U- IOI3
U.
|

g
1(514 I I IIl]lll I II~ll III i i ilitlll i i i i ill
I X JO 19 1017 jo ~8 i0 19 i0 20 Io 21
600 700 800 900 I000 I100 1200
TEMPERATURE I~ BORON CONCENTRATION , ATOMS/ CM 2

Fig. 3. Boron solid solubility vs. temperature Fig. 4. Diffusion coefficient vs. boron concentration

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 1144 J. Electroehem. Soc.: S O L I D S T A T E S C I E N C E A u g u s t 1969
I X l O II i I
tion are represented on Fig. 5 by a data point indicat-
ing the value of the concentration i n d e p e n d e n t coeffi-
cient, together with a vertical line indicating the r a n g e
of values which hold at higher concentrations.

tXt(~ 12 Summary
Values for the solid solubility of boron as a function
of t e m p e r a t u r e i n silicon are presented in this paper
for the first time.
Values of diffusion coefficients for boron in silicon
are given over a r a n g e of t e m p e r a t u r e almost 300~
1•
greater t h a n was previously available (700~176
(9-11). Concentration d e p e n d e n t diffusion coefficients
of boron in silicon are reported.
|
CI | 0 =6.0 X I0 "7 EXP (-38,600) Manuscript s u b m i t t e d Oct. 7, 1968; revised m a n u -
RT script received April 11, 1969.
,3
ixr6"
A n y discussion of this paper will appear in a Dis-
3 cussion Section to be published in the J u n e 1970
JOURNAL.
REFERENCES
1. F. A. Trumbore, Bell Systems Tech. J., 39, 205
i X1(5~5 (1960).
2. K. M. Whittle and G. L. Vick, This Journal, 116,
645 (1969).
3. K. M. Busen, W. A. Fitzgibbons, and W. K. Tsang,
ibid., 115, 291 (1968).
4. E. Kooi, ibid., 111, 1383 (1964).
[XIO 16 I J I I 5. A. E. Owen and P. F. Schmidt, ibid., 115, 548
.6 ,7 ,8 .9 1.0 I.I (1968).
t03/TEMPERATURE ~ 6. E. T a n n e n b a u m , Solid State Electronics, 2, 123
(1961).
Fig. 5. Boron diffusion coefficient vs. temperature 7. J. C. Irwin, Bell Systems Tech. J., 41, 387 (1962).
8. J. 'Crank, "The Mathematics of Diffusion," p. 232,
The diffusion coefficients are plotted against the in- Oxford U n i v e r s i t y Press (1956).
verse of t e m p e r a t u r e in Fig. 5 and can be shown to 9. E. C. Williams, This Journal, 1{)8, 795 (1962).
10. A. D. K u r t z and R. Yee, J. Appl. Phys., 31, 303
follow the equation D = 6.0 x 10 -7 exp(--38600/RT). (1960).
Those diffusion coefficients (above 1000~ for which 11. C. S. F u l l e r and J. A. Ditzenberger, ibid., 27, 544
the coefficients are dependent on i m p u r i t y concentra- (1955).

~|,,,
Technca]l
The Estimation of Bending Stresses from
Flexure Measurements
R. E. Pawel*
Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee

The flexure technique, based on the physical defor-
mation observed w h e n a suitably prepared specimen
is reacted on one side, has recently been employed in
several investigations in which the characterization
and m e a s u r e m e n t of stresses induced by surface or
n e a r - s u r f a c e reactions were of interest. Originally the
tool of the electroplater, this t e c h n i q u e is now being
used in other disciplines to collect special types of
i n f o r m a t i o n which are otherwise difficult to obtain.
Since the principal e x p e r i m e n t a l m e a s u r e m e n t s i n
flexure studies are ones of strain, the problem of t r a n s -
f o r m i n g or assigning appropriate stress values must be
faced. The general methods for doing this have existed
in the l i t e r a t u r e for some time, b u t some u n c e r t a i n t y
has arisen recently concerning the extent and i m p o r -
tance of the Poisson (transverse) contributions d u r i n g
* Electrochemical Society Active Member.
flexure experiments on various kinds of specimens.
(This particular problem is, of course, entirely separate
from the u s u a l l y more tedious one of i n f e r r i n g the
complete stress distribution from the b e n d i n g stress
values.) While it might be argued that this u n c e r t a i n t y
is not a serious d r a w b a c k because of the m a n y other
sources of error involved with the technique, such a
possibility nevertheless w a r r a n t s consideration, and it
is the i n t e n t of the present note to express some
thoughts a n d the results of an e x p e r i m e n t which ap-
pear p e r t i n e n t to the m a n n e r i n which b e n d i n g stresses
are d e t e r m i n e d from b e n d i n g strains.
Since the stress system imposed on the specimen m a y
be considered to be uniform, it is helpful for purposes
of this p r o b l e m to t h i n k only in terms of b e n d i n g
stresses a n d to visualize the surface reaction that cre-
ates them, w h a t e v e r it m a y be, as resulting in simple

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