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Lattice parameter measurements of boron

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ARTICLE in CRYSTAL RESEARCH AND TECHNOLOGY APRIL 2005
Impact Factor: 0.94 DOI: 10.1002/crat.200410361

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Cryst. Res. Technol. 40, No. 4/5, 424 428 (2005) / DOI 10.1002/crat.200410361

Lattice parameter measurements of boron doped Si single crystals

J. Kucytowski and K. Wokulska*
Institute of Materials Science, University of Silesia, ul. Bankowa 12, 40-007 Katowice, Poland
Received 18 May 2004, accepted 29 July 2004
Published online 1 March 2005
Key words silicon single crystals, lattice parameter, boron, oxygen.
PACS 82.80.EJ, 81.05.Cy, 83.85.Hf
The influence of boron dopants and oxygen impurity on lattice parameters of Si single crystals is studied.
Concentrations of boron and oxygen were determined by the Bond method. A linear contraction of the crystal
lattice was observed due to high boron doping of Si single crystals. Lattice parameters of Si single crystals
increased below the lower limit boron concentration NB = 2.1 1016 cm-3. This proves the presence oxygen at
low boron concentrations. In highly boron-doped Si single crystals no oxygen influence on lattice parameter
change was observed.
2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Introduction

Silicon is the best-known and most frequently used semiconductor as a substrate of various electronic devices.
Despite intensive efforts, basic questions about point defects in silicon crystals are still unanswered and hotly
disputed. An attempt to examine the influence of boron impurities on Si single crystals lattice parameter was
undertaken in this study using the Bond method [1], known from previous determination of lattice parameters
of standard Si single crystal with precision a/a = 10-6 [2]. However, to be studied single crystals should have
a high degree of structural perfection. Doping of Si single crystals is known to lead to changes in lattice
parameters [3-8]. Impuritie atoms of radii smaller than the covalent atomic radius of Si (B or P) cause crystal
lattice contraction, while atoms of larger atomic radii (Sb) cause its expansion. Numerous studies have been
carried out on lattice parameter changes due to impurities, their diffusion as well as on the influence of oxygen
micro-precipitations generated during single crystals growing on lattice parameters changes. Several authors
measured the effect of boron doping on silicon lattice deformations [3-8]. The analysis of data for various
boron concentrations in silicon shows that the reported values of the lattice contraction coefficient lie
between 4.5 10-24 cm-3 and 5.5 10-24 cm-3. Table 1 surveys the empirical values of lattice contraction
coefficient of Si crystals in the presence of boron dopants.
Boron atoms most frequently substitute the silicon atoms. As boron atoms are smaller than the covalent
silicon radius, they locally contract the lattice and ultimately cause changes in the relative averaged lattice
parameters:
a/ap = NB,

(1)

where: a/ap is the relative change in the lattice parameter under the influence of impurity, ap is the lattice
parameter of pure and perfect Si single crystal ap = 0.543098367 5.2 10-8 nm (under normal atmospheric
pressure and 20C) [9], and NB is the boron concentration (cm-3).
The influence of boron atom radius 0.088 nm as compared with the covalent radius of silicon atom 0,117
nm, on the lattice constant and unit cell volume change was considered by Celotti et al. [4]. In fact, the boron
atom radius is equal to (0.084 0.001) nm and the covalent silicon radius to (0.118 0.001) nm. Such values
were obtained by Becker [7] from silicon lattice parameter determined with a high accuracy a/a = 1 10-7
____________________

* Corresponding author: e-mail: wokulska@us.edu.pl

2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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425

by the double crystal X-ray technique. He found the lattice contraction coefficient = - 5.6 10-24 cm-3 on the
basis of unit cell volume previously determined by Siegert et al. [10] for high-purity silicon single crystals.
Using a high resolution double-crystal technique Holloway and McCarthy [8] determined coefficient = (-5.19
0.09) 10-24 cm-3 in epitaxial layers of silicon doped with boron (Si:B).
Table 1 Empirically based coefficients of relative lattice changes in Si single crystals due boron doping.
Material
Single crystal of silicon
Single crystal of silicon
Single crystal of silicon
Epitaxial silicon layers
Single crystal of silicon
Silicon epilayers

Boron concentration NB [cm-3]

20

4x10
4x1020
4x1020
< 1x1020
> 1x1018
1.7x1019-1.2x1020

Coefficient [10-24 cm-3]

-4.7
-4.5
-5.0
-6.2
-5.6
-5.19

Reference
[3]
[4]
[5]
[6]
[7]
[8]

Si single crystals are first of all obtained by two methods: the floating zone and the Czochralski method [11].
Dopants as well as trace amounts of undesirable impurities are introduced to them during the growth. Highpurity single crystals both p and n types are frequently obtained by the floating zone method. The resistivity
of Si single crystals obtained by this method is not less than 1000 cm. In this case the concentration of
impurities such as oxygen and carbon does not exceed 5 1016 cm-3, while for other metals it does not exceed 5
1013 cm-3.
Definitely worse Si single crystals are obtained by the Czochralski method. In this case it was found that
oxygen is incorporated to the pulled crystal from molten phase as an impurity. At that time the oxygen
concentration is around 1017 - 1018 cm-3, and the resistivity of such crystals falls to approximately 10-20 cm.
The aim of this paper was to investigate the relation between concentrations of boron dopant moreover
oxygen impurity and the lattice parameter of Si single crystals using the Bond method.

Experimental

A series of 19 p-type (001) oriented Si:B single crystals obtained by the Czochralski method, which differed in
resistivity between 0.03 cm and 40 cm, was studied. Lattice parameters were measured on an asymmetric
reflection 444 CuK1, = 0.15405929 5x10-7 nm [12], using the method of precise measurement of lattice
parameter for perfect crystals the Bond method [1]. For each of them a series of ten measurements of lattice
parameters was made. Statistical analysis of measurement results was carried out. Relative error was a/a = 1
10-6. Lattice parameters were adjusted to 20C, using a linear coefficient of thermal expansion [13]:
= [2.51 + 0.0087(T 293.0) K 0.05] 10-6 K-1.

(2)

Analysis of systematic errors was carried out according to ref. [14]. The contribution of the following factors
causing a shift of the peak position of measuring curve with respect the Bragg angle was considered: X-rays
refraction, X-ray beam horizontal and vertical divergence, absorption in the crystal and others. These
aberrations result in a change in lattice parameters and affect the accuracy of measurements. The total value of
obtained corrections was a = 6.13 10-6 nm.

Results

The interaction of boron atoms with the Si crystal lattice is the basis of effective change in lattice parameters of
the examined Si:B single crystals. The concentration NB of boron atoms in silicon was determined using
relation (1). The coefficient of lattice changes from the values of silicon and impurity atomic radii was
determined from the relation:

RB RSi
,
RSi N

(3)

2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

426

J. Kucytowski and K. Wokulska: Lattice parameter measurements of doped Si single crystals

where: RSi is the Si covalent atomic radius = 0.118 nm [10], RB is the B covalent atomic radius = 0.084 nm [7],
and N is the density of lattice sites = 4.99 1022 cm-3. The calculated value of the coefficient = -5.77 10-24
cm-3 is close to the literature data (Table 1).
Table 2 presents results of lattice parameter measurements for Si:B single crystals and the calculated boron
concentrations NB and boron concentrations determined from resistivity measurements. The comparison of the
results shows excellent agreement between our findings and boron concentrations obtained on the basis of the
resistivity measurements. While determining the boron concentration the lattice parameter of ideal Waso 9
single crystal Si was taken as the standard value, ap = 0.543098367 5.2 10-8 nm, referred to 20C and
normal atmospheric pressure [9]. This single crystal had a perfect structure and lack any of impurities. The
dependence of Si single crystal lattice parameter changes versus boron doping is presented in Fig. 1.
It was ascertained that the lattice parameter falls linearly with increasing boron concentration (between NB
= 2.1 1016 cm-3 and 2.3 1019 cm-3). This proves a strong influence of boron on the silicon crystal lattice and
lack of any defects such as another impurities, striations or agglomerations of point defects. When comparing
relative changes in the lattice parameter a/ap this trend becomes even clearer. Similar relationship for borondoped silicon up to NB = 1 1019 cm-3 was observed by Baribeau and Rolfe [6]. For single crystals of lattice
parameter values close to pure Si measuring points on the diagram a = f(NB) become inseparable. Below the NB
= 5 1016 cm-3 the changes in lattice parameter values are imperceptible.

Table 2 Boron concentrations in silicon single crystals derived from the measured lattice parameter and resistivity
measurements.
Crystal

a 1x10-6 [nm]

High pure Sip [9]

1
2
3
4
5
6
7
8
9
10
11
12

0.5430983675.2x10-8
0.5430245
0.5430387
0.5430492
0.5430720
0.5430798
0.5430811
0.5430897
0.5430949
0.5430977
0.5430982
0.5430979
0.5430983

NB concentration from
Bond method [cm-3]
2.3 1019
1.9 1019
1.5 1019
8.4 1018
5.9 1018
5.5 1018
2.7 1018
1.1 1018
2.1 1017
5.3 1016
1.5 1017
2.1 1016

a/ap

NB concentration from
resistivity measurements [cm-3]

-1.4 10-4
-1.1 10-4
-9.1 10-5
-4.9 10-5
-3.4 10-5
-3.2 10-5
-1.6 10-5
-6.4 10-6
-1.2 10-6
-3.1 10-7
-8.6 10-7
-1.2 10-7

3.62 1019 - 2.01 1019

2.61 1019 - 1.62 1019
2.01 1019 - 1.34 1019
1.23 1019 - 8.49 1018
9.08 1018 - 5.97 1018
6.65 1018 - 4.47 1018
4.89 1018 - 3.02 1018
2.33 1018 - 1.40 1018
1.46 1018 - 9.14 1017
9.46 1017 - 5.89 1017
6.05 1017 - 3.88 1017
4.25 1017 - 2.77 1017

Fig. 1 Lattice parameters as a function of

boron concentration.

2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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427

Starting from Si crystal no 13 (Table 3), further increase in the lattice parameter was observed as against the
parameter of standard single crystal Sip = 0.543098367 5.2x10-8 nm. This should be connected with the
presence of oxygen in single crystals examined. Results for Si single crystals no 13-19 and the oxygen
concentration NO determined from relation (1) are presented in Table 3. To determine the oxygen concentration
NO, the lattice expansion coefficient O = 4.4 10-24 cm-3 for oxygen given by Windisch and Becker [9] was
used.
As shown in Table 3 and Fig. 2, the increase in lattice parameters results from the increase in oxygen
concentration in single crystals studied here.
Table 3 The oxygen concentrations in silicon single crystals derived from the lattice parameter
measurements.
Crystal
High pure Sip[9]
13
14
15
16
17
18
19

a 1x10-6 [nm]
0.543098367 5.2 10-8
0.5430989
0.5430993
0.5431019
0.5431006
0.5431011
0.5431010
0.5431005

NO [cm-3]
2.2 1017
3.9 1017
1.5 1018
9.3 1017
1.1 1018
1.1 1018
8.9 1017

a/ap
9.8 10-7
1.7 10-6
6.5 10-6
4.1 10-6
5.0 10-6
4.9 10-6
3.9 10-6

Fig. 2 Relationship between

change of the lattice parameter
and the oxygen concentration.

As in highly boron-doped Si single crystals no influence of oxygen on lattice parameter changes was observed,
and at lower concentration the crystal lattice expanded as compared with the standard single crystal, it proves
the reactions proceeding during the crystallisation. Abe et al. [15] found that during the growth of single
crystals obtained by the Czochralski method oxygen is incorporated to the crystal from the molten phase as an
impurity originating from quartz crucible. Oxygen from the quartz crucible transfers to the molten Si up to the
solubility limit. At the same time silicon monoxides and other oxides of dopants (B, Sb) evaporate, depending
on their partial pressures. In highly boron-doped Si single crystals, boron can react with SiO thereby enhancing
the evaporation of SiO when pulling Si crystal. This results in a reduction of the oxygen concentration, which
leads to values undetectable in lattice parameters measurements by the Bond method (Table 2).
While comparing the results in Table 2 one aspects that lattice parameter measurements of high boron
concentration Si single crystals by the Bond method are more accurate than the resistivity measurements. For
the determination of boron concentration from the silicon resistivity the results obtained by the American
Society for Testing and Materials ASTM [16] were used. Only close to the threshold of impurities detectability
by the Bond method (i.e. below the concentration of 5 1016 cm-3) the NB values predicted by the Bond
method are lower than those from resistivity measurements.
2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

428

J. Kucytowski and K. Wokulska: Lattice parameter measurements of doped Si single crystals

Summary

On the basis of precise and accurate measurements of lattice parameters of the boron and oxygen
concentrations in Si single crystals obtained by Czochralski method was determined. It is concluded that the
cause of the lattice contraction within the range a = 0.5430245 0.5430983 nm is immediately attributed to
the presence of substitutional boron in the silicon crystal lattice.
A prevailing nonintentionally impurity in silicon crystals, oxygen, may also contribute to alter the lattice
parameters. In this case the oxygen is incorporated into the silicon lattice occupying interstitial sites and
causing a lattice expansion. It has been ascertained that in highly boron-doped Si single crystals no oxygen
influence on lattice parameter change was observed. Only below the boron concentration NB = 2.1 1016 cm-3
the presence of oxygen within the range NO = 2.2 1017 1.5 1018 cm-3 was observed.
Acknowledgements The authors wish to thank Mrs B. Surma from the Institute of Electronic Materials Technology in
Warsaw for supplying the single crystals and for fruitful discussions.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]

W. L.Bond, Acta Cryst. 13, 814 (1960).

J. Hrtwig, J. Bk-Misiuk, H. Berger, H.- G. Brhl, Y.Okada, S. Grosswig, K. Wokulska, and J. Wolf, Phys. Stat.
Sol. (a) 142, 19 (1994).
S. Kishino, Adv. X-ray Anal. 16, 367 (1973).
G. Celotti, D. Nobili, and P. Ostoja, J. Mater. Sci. 9, 821 (1974).
A. Fukuhara and Y. Takano, Acta Cryst. A 33, 137 (1977).
J. Baribeau and S. Rolfe, Appl. Phys. Lett. 58, 2129 (1991).
P. Becker in Proc. VII Intern. School on Defects in Crystals, World Scientific, Singapore 1987, p. 118.
H. Holloway and S. L. McCarthy, J. Appl. Phys. 73, 103 (1993).
D. Windisch and P. Becker, Phys. Stat. Sol. (a) 118, 379 (1990).
H. Siegert, P. Becker, and P. Seyfried, Z. Physik B 56, 273 (1984).
J. mija, Fundamentals of Single Crystals Growth Theory, PWN, Warszawa, 1987.
G. Hlzer, M. Fritsch, M. Deutsch, J. Hrtwig, and E. Frster, Phys. Rev. A 56, 4554 (1997).
Y. Okada and Y. Tokumoru, J. Appl. Phys. 56, 314 (1984).
J. Hrtwig and S. Grosswig, Phys. Stat. Sol. (a) 115, 369 (1989).
K. Abe, K. Terashima, T. Matsumoto, S. Maeda, and H. Nakanishi, J. Cryst. Growth 186, 557 (1998).
Standard Practice for Conversion between resistivity and dopant density for boron-doped and phosphorus-doped
silicon, Annual Book of ASTM, F 723-81, 590 (1982).

2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim