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SUPPLEMENTARY INFORMATION
Ternary intermetallic compounds in Au-Sn soldering systems – structure and properties
(Submitted to Journal of Materials Science)
CAROLA J. MÜLLER,1,2 VOLODYMYR BUSHLYA,3 MASOOMEH GHASEMI,4 SVEN LIDIN,1 MARTIN
VALLDOR5,6 and FEI WANG1
1.—Lund University, Centre for Analysis and Synthesis, Box 124, 22100 Lund, Sweden. 2. —E-Mail:
[email protected] 3.—Lund University, Production and Materials Engineering, Box 118, 22100 Lund,
Sweden. 4.—Lund University, Solid State Physics, Box 118, 22100 Lund, Sweden. 5.—University Cologne, II.
Physikalisches Institut, Zülpicher Str. 77, 50937 Cologne, Germany. 6.—Current address: Max-Planck-Institute for
Chemical Physics of Solids, Nöthnitzer Str. 40, 01187 Dresden, Germany
S1: Powder X-Ray Diffraction
Herein, we would like to present additional figures that support the statements in the paper.
Fig. S1: PXRD patterns for Au3InSn2 after different heat treatments. Notably, the different annealing
temperatures do not affect the c/a ratios of the compound. Left: Complete measurements; Right: Selected
angular range around the strongest reflection.
Fig. S2: PXRD patterns for samples of different compositions Au:In:Sn. The pattern for AuSn was
calculated from the reported crystal structure by Jan and coworkers [13]. The results indicate that there is
a continuous solid solution of In in the binary compound AuSn. The maximum solid solubility is reached in
Au3InSn2. Left: Complete measurements; Right: Selected angular range around the strongest reflection. It
is apparent that the lattice parameters are changing anisotropically because there is no constant shift of
the positions of the reflections.
Fig. S3: PXRD patterns for samples of different compositions Au:In:Sn. The pattern for Au 3In2 was
calculated from the reported crystal structure by Schubert and coworkers [19]. It is shown how extra
reflections of AuIn and Au3In2 appear in samples whose compositions are on lines from Au 3InSn2-AuIn
(constant content of Au of 50 at.-%) and Au3InSn2-Au3In2 (increasing Au and In contents). In agreement
with Borzone et.al. [15,16], these results indicate that the full solubility of elemental In in the compound
AuSn is reached at the composition Au3InSn2.
Fig. S4: PXRD patterns for samples of different compositions Au:In:Sn. It is shown how extra reflections
(green arrows) appear on increasing the Au content in the samples, i.e. constant In:Sn ratio. .
Fig. S5: PXRD patterns for samples of different compositions Au:In:Sn. The extra reflections that are very
weak in Fig. S4 are in fact two extra phases: Au3In and Au5Sn. .Remarkably, the observed peak positions
do neither correspond to the binary compounds Au7In3 nor Au9In4. As a conclusion, these compounds do
not dissolve any elemental Sn.
Fig. S6: PXRD pattern for a sample of a different composition Au:Sn:Sb, Au3Sn3Sb. The extra reflections
correspond to two extra phases: AuSb 2 and Au5Sn. This result is indicating that a composition Au 6Sn5Sb
represents the maximum solid solubility range of Sb in AuSn.
S2: Single Crystal Diffraction
In the following section, details on the results from single crystal X-ray diffraction are given.
Fig. S7: SCXRD: Lattice parameters and c/a ratios of Au3InxSn3-x; for comparison Au6Sn5Sb and Au3In2
are depicted as well [13,19]. The unannealed sample is indicated by the square.
Table S1. Experimental details for SCXRD.
Annealing Temperature (K) oven cooling
373
473
573
Chemical formula, nominal Au3In1Sn2
Au3In1Sn2
Au3In1Sn2
Au3In1Sn2
Chemical formula, refined AuIn0.1Sn0.9
AuIn0Sn
AuIn0Sn
AuIn0Sn
Mr
315.3
315.7
315.7
315.7
Crystal system, space
Hexagonal, P63/mmc, 2
group, Z
Temperature (K)
293
293
293
293
a, c (Å)
4.2857 (5),
4.2858 (2),
4.2843 (2),
4.2861 (3),
5.5455 (5)
5.5436 (2)
5.5449 (2)
5.5430 (4)
V (Å3)
88.21 (2)
88.18 (1)
88.14 (1)
88.19 (1)
Radiation type
Mo Kα
Mo Kα
Mo Kα
Mo Kα
µ (mm−1)
96.50
96.64
96.69
96.63
Crystal size (mm)
0.11 × 0.06 × 0.03
0.11 × 0.04 × 0.02
0.08 × 0.04 × 0.03
0.07 × 0.04 × 0.02
Diffractometer
Xcalibur, Eos diffractometer
Absorption correction
Analytical
CrysAlis PRO, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014
CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Analytical numeric absorption
correction using a multifaceted crystal model based on expressions derived by R.C.
Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Tmin, Tmax
0.025, 0.141
0.024, 0.194
0.036, 0.146
0.033, 0.148
No. of measured,
1140, 56, 52
1089, 56, 52
832, 55, 52
931, 55, 51
Rint
0.116
0.170
0.095
0.091
(sin θ/λ)max (Å−1)
0.663
0.663
0.649
0.648
R[F2 > 2σ(F2)], wR(F2), S
0.021, 0.045, 1.61
0.031, 0.079, 2.74
0.018, 0.045, 1.70
0.022, 0.053, 1.96
reflections/ parameters
56 / 7
56/ 6
55/ 6
55 /7
Δρmax, Δρmin (e Å−3)
1.60, −2.08
3.35, −3.35
1.85, −1.97
2.22, −5.46
independent and
observed [I > 3σ(I)]
reflections
Table S2. Experimental details for SCXRD.
Annealing temperature (K) 673
oven cooling
oven cooling
623
Au3In0.33Sn2.67
Au3In0.67Sn0.33
Au6Sn5Sb1
Chemical formula, refined AuIn0Sn
AuIn0Sn
AuIn0Sn
AuSnSb0
Mr
315.7
315.7
315.7
315.7
Crystal system, space
Hexagonal, P63/mmc, 2
Chemical formula,
nominal
Au3In1Sn2
group, Z
Temperature (K)
293
293
293
293
a, c (Å)
4.2869 (2),
4.3075 (8),
4.2974 (2),
4.3429 (2),
5.5448 (3)
5.5300 (9)
5.5392 (3)
5.5183 (3)
V (Å3)
88.25 (1)
88.86 (3)
88.59 (1)
90.14 (1)
Radiation type
Mo Kα
Mo Kα
Mo Kα
Mo Kα
µ (mm−1)
96.57
95.90
96.20
94.55
Crystal size (mm)
0.07 × 0.04 × 0.03
0.10 × 0.04 × 0.03
0.08 × 0.06 × 0.02
0.13 × 0.09 × 0.06
Diffractometer
Xcalibur, Eos diffractometer
Absorption correction
Analytical
CrysAlis PRO, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014
CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Analytical numeric absorption
correction using a multifaceted crystal model based on expressions derived by R.C.
Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Tmin, Tmax
0.045, 0.218
0.02, 0.153
0.019, 0.164
0.015, 0.067
measured, independent
1166, 55, 52
1328, 56, 53
1312, 56, 52
1162, 56, 54
Rint
0.112
0.128
0.097
0.094
(sin θ/λ)max (Å−1)
0.648
0.662
0.662
0.659
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.052, 2.03
0.020, 0.049, 1.78
0.020, 0.054, 2.02
0.033, 0.071, 2.98
reflections/ parameters
55/ 6
56/ 7
56/ 7
56/ 6
Δρmax, Δρmin (e Å−3)
2.74, −2.53
1.85, −2.63
2.15, −4.23
3.99, −4.16
and
observed [I > 3σ(I)]
reflections
S3: Thermal Analysis
Fig. S8 Liquidus projections of the Au-Sb-Sn
ternary system are extrapolated from the subbinaries [55]. The Au6Sn5Sb composition is
shown with the red circle. The arrows indicate
the crystallization path for this composition. The
primary crystallization field is AuSn. Next, the
AuSb2 phase precipitates. Finally, Au5Sn forms
through a eutectic reaction.
Fig. S9 The AuSn-AuIn vertical section of the
Au-In-Sn ternary system is calculated using the
assessed parameters by Cacciamani et al. [16].
On cooling from the nominal composition of
Au0.5In0.167Sn0.333, the primary crystallization field
is AuSn at 749 K.