Crystallographic study of the intermediate compounds SbZn, Sb3Zn4 and Sb2Zn3

Article abstract of DOI:10.1016/j.jallcom.2005.09.068

The processes of development of semiconductor ceramics made up of bismuth, antimony and zinc often require during their preparation to know the nature of the involved phases. For that, it is always essential to refer to the diagrams of balance between pha

Full text of DOI:10.1016/j.jallcom.2005.09.068

Journal of Alloys and Compounds 419 (2006) 267–270
Crystallographic study of the intermediate compounds
SbZn, Sb Zn and Sb Zn
3
4
2
3
∗
Fouzia Adjadj, El-djemai Belbacha , Malek Bouharkat, Abdellah Kerboub
Laboratoire des e´ tudes Physico-chimiques des Mat e´ riaux, D e´ partement de Physique, Facult e´ des Sciences,
Universit e´ de Batna, 05000 Batna, Algeria
Received 8 August 2005; accepted 4 September 2005
Available online 15 November 2005
Abstract
The processes of development of semiconductor ceramics made up of bismuth, antimony and zinc often require during their preparation to know
the nature of the involved phases. For that, it is always essential to refer to the diagrams of balance between phases of the binary systems or ternary.
We presented in this work the study by X-rays diffraction relating to the intermediate compounds SbZn, Sb
X-rays is often useful to give supplement the results of the other experimental methods.
3 4 2 3
Zn and Sb Zn . The analysis by
©
2005 Elsevier B.V. All rights reserved.
Keywords: X-rays; SbZn; Sb3Zn4; Sb2Zn3
1
. Introduction
The Sb3Zn4 compound is of congruent fusion at the temper-
ature 566 C and exists in two allotropic forms ␤ and ␥.
◦
Some alloys of bismuth, antimony and zinc are semiconduc-
The Sb2Zn3 compound, is also of congruent fusion at the
◦
tor ceramics precursors. To fix a protocol of their preparation,
it is necessary to have a thorough knowledge of their phase dia-
gram. After a first study concerning the Bi–Zn system [1,2] and
the study of two isothermal cuts in the Bi–Sb–Zn system [2] the
experimental study of the Sb–Zn system has been undertaken
because of the very controversy results found in the bibliogra-
phy [3,4]. In the Sb–Zn system, appear three intermediate phases
SbZn, Sb3Zn4 and Sb2Zn3. These compounds were character-
ized by means of the X-rays diffraction on powder.
temperature 568 C and exists in two forms ␩ and ␨. The latter
◦
breaks up at about 360 C according to a reaction of the form:
3Sb2Zn3 (␨) ↔ 2Sb3Zn4(␤) + Zn. The reverse reaction occurs at
◦
about 407 C.
3
. Experimental procedure and used materials
TheidentificationofphasesbyX-raysdiffractionhasbeencarriedPHILLIPS
PW1877Version3.5diffractometer. Forthehightemperaturetests, wehaveused
a SIEMENS apparatus. The samples are reduced to a fine powder (<250 ␮m).
This powder is then put on a glass plate. To avoid the risks of oxidation in the
ambient air, a collodion drop is put on the surface. The indexing of the reflexions
has been carried out starting from the inter-reticular distances from the X-rays
diffraction diagram the refinement of the lattice parameters has been carried out
by the least square method. Zinc is a Carlo Erba product containing less than
0.08% of impurities. Antimony is an Aldrich production of a content of 99.8%.
2
. Bibliographical analysis
The study of the phase diagram of the Sb–Zn system has been
undertaken by many authors [5–18]. Their results are often very
unmatched. The experimental study that we carried out made it
possible to highlight three compounds.
The SbZn compound is stoechiometric, it breaks up at
the temperature 544 C according to the peritectic reaction:
4. Results and discussion
◦
SbZn ↔ Liq. + Sb3Zn4(␤).
The alloys to be analyzed by X-rays diffraction are recovered
from the samples having undergone a calorimetric analysis in
order to build the diagram phases of the Sb–Zn system. We
separately present the results obtained for each compound.
∗
Corresponding author.
E-mail address: Beldjem@caramail.com (E.-d. Belbacha).
0
925-8388/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2005.09.068

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F. Adjadj et al. / Journal of Alloys and Compounds 419 (2006) 267–270
Table 1
Table 2
Analysis results by X-rays diffraction of SbZn
Indexation in the orthorhombic system Sb3Zn4
h k l d Measured d Calculated
0 0 1 10.9286
2θ
I/I0
d Measured
I/I0
18.83
2
2
2
2
3
3
3
3
3
4
4
4
5
5
6
6
6
4.94
5.96
8.44
9.04
0.72
2.76
4.86
6.24
8.54
3.04
3.80
5.82
0.34
0.58
3.74
3.88
5.56
34.53
3.5702
3.4322
3.1383
3.0748
2.9103
2.7336
2.5736
2.4787
2.3359
2.1015
2.0668
1.9803
1.8126
1.8045
1.4601
1.4572
1.4239
11.3158
7.3453
3.7841
3.7719
3.9139
3.4933
3.5232
3.4141
3.3554
3.3399
3.3639
3.0805
3.0960
2.9908
2.8289
2.7100
2.6682
2.6768
2.5747
2.5150
2.4484
2.4441
2.4551
2.2934
2.2982
2.1247
2.0884
2.0904
2.0557
2.0206
2.0076
1.9570
1.9609
1.9267
1.9366
1.9042
1.8860
1.8920
1.8735
1.8797
1.8765
1.7901
1.7841
1.7812
1.7616
1.7070
1.6777
1.6812
1.6823
1.6820
1.6172
1.5638
1.5403
1.5381
1.5120
1.5143
1.4487
1.4334
1.3437
1.3403
1.3454
58.27
100.00
94.24
11.51
64.75
18.71
20.86
17.99
15.83
72.66
37.41
23.02
24.46
11.51
25.18
17.99
0 1 0
2 0 1
0 0 3
1 1 2
0 2 1
2 1 0
1 0 3
0 1 3
1 2 0
2 1 1
0 2 2
1 1 3
2 1 2
0 0 4
2 2 0
1 0 4
7.2605
3.8453
3.8453
3.8453
3.5079
3.5790
3.4076
3.3448
3.3448
3.3448
3.0883
3.0883
2.9641
2.8444
2.7008
2.6664
2.6664
2.5488
2.5488
2.4481
2.4481
2.4481
2.3020
2.3020
2.1256
2.0727
2.0727
2.0619
2.0312
2.0098
1.9549
1.9549
1.9321
1.9321
1.9069
1.8905
1.8905
1.8744
1.8744
1.8744
1.7969
1.7493
1.7493
1.7608
1.7107
1.6783
1.6783
1.6783
1.6783
1.6179
1.5667
1.5383
1.5383
1.5155
1.5155
1.4501
1.4307
1.3439
1.3439
1.3439
18.39
14.35
14.35
14.35
98.65
98.65
80.27
72.20
72.20
72.20
29.15
29.15
100.0
37.22
19.28
29.60
29.60
4.93
3
2
3
0
2
3
1
0 0
1 3
1 0
3 0
2 2
1 1
3 1
4.93
4
.1. SbZn compound
In Table 1, we have reported the numerical results of the
91.93
91.93
91.93
13.00
13.00
64.57
8.97
analysis by X-rays diffraction of about the SbZn compound.
This last has been already studied [12] and our results are in
good agreement with those of the bibliography, we think that
useless to reindex this compound.
3 1 2
3
1
2
2
2 1
1 5
3 0
3 1
8.97
32.29
47.53
89.69
44.39
44.39
13.45
13.45
17.94
15.70
15.70
23.77
23.77
23.77
07.62
10.76
10.76
13.45
10.76
15.70
15.70
15.70
15.70
08.97
7.17
4
.2. Sb3Zn4 compound
3 2 2
4
2
2
0
4
0 0
2 4
3 2
2 5
1 0
In Table 2, we recomputed the inter-reticular distances
indexed in the orthorhombic system and which are concordant
with those of Psarev and Dobryden [12]. The latter indexed
it in the same network and obtain the following parameters:
2 1 5
0 0 6
˚
˚
˚
a = 7.981 A, b = 7.495 A, c = 10.72 A. In Fig. 1 we illustrated the
4
1
3
3
1
0 2
2 5
1 4
2 3
4 0
X-rays of diffraction diagram of Sb3Zn4.
4
.3. Sb2Zn3 compound
It has been not possible to us to obtain for this compound the
3 3 1
1
4
2
0
2
3
4
1
3
0
4
5
3
5
1
2
2
4
1 6
2 0
0 6
2 6
3 4
1 5
2 2
4 3
2 5
4 4
3 1
1 2
4 0
1 3
5 1
4 5
5 2
4 1
X-rays diffraction diagram described by Dobryden and Psarev
12] or Lapkina et al. [16] even under exactly the same operating
[
conditions. The former study the diagram, after water quenching
13.90
13.90
15.25
15.25
16.59
11.66
12.11
12.11
12.11
a = (8.03 ± 0.01) A˚ ; b = (7.34 ± 0.01) A˚ ; c = (11.31 ± 0.02) A˚ .
Fig. 1. X-rays diffraction diagram of Sb3Zn4.

F. Adjadj et al. / Journal of Alloys and Compounds 419 (2006) 267–270
269
◦
◦
of alloy of Sb2Zn3 composition, from the temperature 420 C.
The latter operate differently, they maintain the alloy at 440 C
for 350 h and soak it. All the tests we carried out lead to the
same result. The alloy Sb2Zn3 always break up into a mixture
of Zn and Sb3Zn4. We reproduced (Fig. 2) an example of the
X-rays diffraction diagram for Sb2Zn3 alloy molten and then
slowly cooled.
In a second series of experiences, we tried to show the
formation of the Sb2Zn3 phase by gradually reheating this
◦
◦
compound from 100 to 480 C with 10 C as a step and plot for
every step the X-rays diagram. The operations are carried out
Table 3
Fig. 2. X-rays diffraction diagram of Sb2Zn3.
Indexation in the orthorhombic system Sb2Zn3
h k l
d Measured
d Calculated
I/I0
12.24
under nitrogen sweeping. As the temperature increases, Sb3Zn4
diagram disappears and that of the zincite ZnO appears. It
seems that the circulating gas contains oxygen traces involving
a phenomenon of oxidation starting from the temperatures of
phase shift. In order to compare the diagram of this alloy with
that of Sb Zn , we recomputed in the orthorhombic system the
0
0
2
1
0
1
2
0
2
0
1
3
0
2
3
1
3
3
1
2
2
3
4
2
2
0
2
0
4
1
3
3
3
1
4
2
0
2
3
4
1
0
4
5
3
5
1
0 1
2 1
1 0
0 3
1 3
2 0
1 1
2 2
1 2
0 4
0 4
0 0
3 0
2 2
1 1
3 1
1 2
2 1
1 5
3 0
3 1
2 2
0 0
2 4
3 2
2 5
1 5
0 6
0 2
2 5
1 4
2 3
3 1
1 6
2 0
0 6
2 6
3 4
1 5
2 2
4 3
4 4
3 1
1 2
4 0
1 3
5 1
11.3050
3.5079
3.5079
3.4076
3.3448
3.3448
3.3448
3.0511
2.9641
2.8444
2.6664
2.6664
2.4481
2.4481
2.4481
2.3009
2.3009
2.1265
2.0836
2.0836
2.0628
2.0312
2.0106
1.9541
1.9541
1.9206
1.9069
1.8913
1.8913
1.8759
1.8759
1.8759
1.7819
1.7859
1.7608
1.7107
1.6800
1.6800
1.6800
1.6800
1.6190
1.5397
1.5397
1.5151
1.5151
1.4473
1.4303
11.3217
3.4910
3.5236
3.4158
3.3562
3.3378
3.3644
3.0791
2.9914
2.8304
2.6696
2.6779
2.4463
2.4438
2.4558
2.2918
2.2989
2.1247
2.0892
2.0893
2.0546
2.0206
2.0084
1.9571
1.9601
1.9270
1.9049
1.8870
1.8928
1.8738
1.8803
1.8767
1.7836
1.7820
1.7618
1.7079
1.6781
1.6810
1.6830
1.6822
1.6163
1.5396
1.5379
1.5125
1.5136
1.4492
1.4323
100.0
100.0
50.53
45.10
45.10
45.10
5.94
3
4
inter-reticular distances. The results are deferred in Table 3.One
obtains most of the computed lines of the compound Sb3Zn4.
59.79
30.07
17.48
17.48
76.92
76.92
76.92
13.64
13.64
40.91
13.99
13.99
20.63
52.80
69.58
27.62
27.62
4.20
15.73
12.59
12.59
16.08
16.08
16.08
6.29
6.29
13.64
9.79
5. Conclusion
Following several experimental studies of the binary systems
Bi–Zn and Sb–Zn and ternary systems Bi–Sb–Zn for the devel-
opment of semiconductor ceramics, we were interested in the
analyses by diffraction of X-rays in several fields of phases and
for certain intermediaries. In this work, we present the analysis
results by X-rays diffraction of obtained by studying the inter-
mediate compounds SbZn, Sb3Zn4 and Sb2Zn3 existing in the
diagram of balance between phases of the Sb–Zn binary system.
Concerning the SbZn compound, our results agree perfectly with
those of the literature. For the Sb3Zn4 compound, we indexed
it in the orthorhombic system and its definite lattice parameters.
As for Sb2Zn3, it was impossible to obtain a diffraction diagram
specific to this compound since it does not exist at ambient tem-
perature. It always breaks up into Zn and Sb3Zn4.
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