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Solid State Communications 151 (2011) 947951

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Solid State Communications

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X-ray diffraction, Raman spectrum and magnetic susceptibility of the magnetic

semiconductor Cu2 FeSnS4
C. Rincn a, , M. Quintero a , E. Moreno a , Ch. Power a , E. Quintero a , J.A. Henao b , M.A. Macas b ,
G.E. Delgado c , R. Tovar a , M. Morocoima a
a

Centro de Estudios de Semiconductores, Departamento de Fsica, Facultad de Ciencias, Universidad de Los Andes, Mrida 5101, Repblica Bolivariana de Venezuela

Grupo de Investigacin en Qumica Estructural, Facultad de Ciencias, Escuela de Qumica, Universidad Industrial de Santander, Apartado Areo 678, Bucaramanga, Colombia

Laboratorio de Cristalografa, Departamento de Qumica, Facultad de Ciencias, Universidad de Los Andes, Mrida 5101, Repblica Bolivariana de Venezuela

article

info

Article history:
Received 13 March 2011
Accepted 4 April 2011
by M. Grynberg
Available online 16 April 2011
Keywords:
A. Semiconductors
C. Crystal structure and symmetry
C. X-ray scattering
D. Raman scattering

abstract
In an attempt to resolve the crystal structure and the corresponding space group of the magnetic
semiconductor Cu2 FeSnS4 , samples of this compound were studied by X-ray diffraction, differential
thermal analysis, Raman scattering and magnetic susceptibility. It was found that at room temperature
this compound prepared by a careful crystal growth process, including annealing to equilibrium at a
suitable temperature followed by slow cooling of the samples to 300 K, crystallizes in a tetragonal

structure with space group P 4.

2011 Elsevier Ltd. All rights reserved.

1. Introduction
The quaternary semiconductor Cu2 FeSnS4 , which belongs to
the family of Cu2 BII CIV XVI
4 compounds, has received considerable
attention not only due to its motivating magnetic properties
[13] but also because of the interest in relation to the occurrence
of stannite and/or kesterite crystalline structures along the
pseudo-binary section of Cu2 FeSnS4 Cu2 ZnSnS4 alloy system
[4,5]. It has been reported that for T > 706 C a complete
solid solution extends across this section as a phase labeled
as -Cu2 (FeZn)SnS4 [4]. As determined from X-ray analysis,
synthesized samples of -Cu2 FeSnS4 quenched from temperatures
higher than 750 C crystallizes in the stannite structure [4,5].
Below 706 C, this phase transforms to a different not-wellknown structure -Cu2 FeSnS4 [4]. It has also been established
[6,7] that natural Cu2 FeSnS4 samples crystallize in the stannite
structure. However, a controversy exists about the crystal structure
and the space group of the synthesized low-temperature phase
of Cu2 FeSnS4 . In fact, cubic (P43m) [8], tetragonal kesterite
(I-4) [9] or stannite [10] and P4 [11] structures have been
proposed for this -phase. Thus, the problem of the crystal
structure and its space group of synthesized -Cu2 FeSnS4 remains
unsolved. Also, in most of the works devoted to establish the

Corresponding author. Tel.: +58 0274 2401306; fax: +58 0274 2401286.
E-mail address: crincon@ula.ve (C. Rincn).

0038-1098/$ see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ssc.2011.04.002

crystalline structure of this material, no detailed information

related to the preparation of Cu2 FeSnS4 samples and their
exact heat treatment is given. This is a crucial point mainly
because phase diagrams of multinary compounds and their alloys
revealed [12] that several ordereddisordered transitions, which
occur even at relatively low temperatures, are usually present
in these materials. Thus, in general, the crystal structure of
the samples obtained depends on the temperature range where
the crystal growth process is performed [13]. In an attempt to
resolve the crystal structure and the corresponding space group
of the synthesized -Cu2 FeSnSe4 phase, crystals of this phase
were prepared. The crystals thus obtained were studied by Xray diffraction data, differential thermal analysis (DTA), Raman
scattering and magnetic susceptibility ( ). It is concluded that
-Cu2 FeSnS4 samples with the tetragonal P 4 structure can be
obtained by using a careful crystal growth process which includes
annealing to equilibrium at a suitable temperature followed by
slow cooling of the samples to room temperature.
2. Crystal growth and experimental details
Cu2 FeSnS4 samples were grown from the melt. The components
of 1.0 g sample, sealed under vacuum in a quartz ampoule, were
heated up to 200 C and kept at this temperature for 2 h. The
ampoule was then raised to 500 C using a rate of 40 K/h and held
at this temperature for 14 h. After, in order to melt the components,
samples were heated from 500 to 800 C at a rate of 30 K/h and

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C. Rincn et al. / Solid State Communications 151 (2011) 947951

kept at this temperature for another 14 h. Then, they were raised

at 60 K/h to 1300 C and maintained at this temperature for 2 h. The
furnace temperature was brought slowly (4 C/h) down to 600 C
and the samples were annealed for 1 month. Finally, they were
slowly cooled to room temperature using a rate of about 2 K/h. The
resulting as-grown samples were investigated by X-ray powder
diffraction. Details of the experimental equipment, analysis for
the indexing of the X-ray diffraction patterns, estimation of
lattice parameters and determination of the space group by
using standard computer programs is given elsewhere [14]. The
chemical analysis of Cu2 FeSnSe4 samples, as performed by energy
dispersive X-ray spectroscopy, gave the atomic percentage average
chemical composition of Cu:Fe:Sn:S ratio as 26.0:13.3:13.5:47.1,
close to the ideal value 2:1:1:4. The error in the analysis was
around 3%. Phase transition temperatures were obtained from
DTA measurements using a Perkin Elmer DTA-7 equipment.
Raman spectrum of the compound at room temperature in the
backscattering configuration was recorded by using a confocal
Dilor XY800 triple spectrometer equipped with a liquid-nitrogencooled charge-coupled detector. The 514.5 nm line of an Ar-ion
laser was used as excitation source and the spectral resolution
was 1.0 cm1 . Measurements of vs. T in the temperature range
from 2 to 300 K were made by using a quantum design SQUID
magnetometer.
3. Experimental results and discussion
3.1. X-ray powder diffraction analysis
Since several crystal structures and the corresponding space
groups have been proposed for the -Cu2 FeSnS4 phase, in the
present X-ray data analysis the refining of its crystal structure
by the Rietveld method was performed by considering several
space groups in the tetragonal and cubic structures. The best
fit was obtained for a tetragonal structure with the P4 space
group, in agreement with that reported in [11]. This is observed in
Fig. 1 where the experimental and calculated powder diffraction
patterns and their difference for this structure are shown. The
results of the analysis are shown in Tables 1 and 2. To explain
the existence at room temperature of both -Cu2 FeSnS4 and
-Cu2 FeSnS4 modifications, the phase relations in this compound
should be considered. Thus, in the DTA cooling thermogram for the
present compound shown in Fig. 2, in addition to the melting point
which occurs at 831 C, a first order solidsolid phase transition
is observed at 702 C indicating that a crystalline structural
transformation from -Cu2 FeSnS4 (stannite) to -Cu2 FeSnS4 (P4)
occurs at this temperature. This phase transition shows that the
low energy structure of synthesized Cu2 FeSnS4 corresponds to
the lower symmetry tetragonal P4 phase. The high-temperature
-Cu2 FeSnS4 (stannite) phase appears at room temperature
because it could be quenched during the crystal growth process.
It is then expected that samples of Cu2 FeSnS4 rapidly cooled to
room temperature could crystallize in the high symmetric I42m
structure, as has been reported earlier [6,7], while those carefully
cooled to this temperature form in the tetragonal P4 structure.
3.2. Vibrational analysis and Raman spectrum of P4-Cu2 FeSnS4
The factor group analysis of the allowed zone-center vibrations
for the P4 tetragonal crystallographic structures of Cu2 FeSnS4 ,
shown in Table 3, indicates that twenty-one Raman, seventeen
IR, and three acoustic active phonon modes of irreducible
representations: 4A + 5B + 6E1 + 6E2 , 5B + 6E1 + 6E2 , and
1B + 1E1 + 1E2 , respectively, are expected for this compound.
An unpolarized Raman spectrum of P4-Cu2 FeSnS4 at 300 K
is shown in Fig. 3. After its deconvolution by a Lorentzian line

Table 1
Rietveld refinement details for Cu2 FeSnS4 .
Molecular formula

Cu2 FeSnS4

a and b ()
c ()

5.4329(3)
5.4104(2)

V ( )
Z
Space group
Dx (g/cm3 )
Rw
RB
Rexp

159.70
1
P4 (N 81)
4.47
5.37
4.27
3.19
1.69
D8-focus bruker
Cu-K : = 1.5406
295
270
32
0.02
6
3400
Pseudo-Voigth

Diffractometer
Radiation monochromator
Temperature (K)
Data range 2 ()
No. refined parameters
Step size ()
Counting time (s/step)
Number of step intensities
Peak-shape profile

Table 2
Atomic coordinates, selected bond distances, and angles for P4-Cu2 FeSnS4 .
2

Atom

Ox.

Site.

Foc

Biso ( )

Cu
Fe
Sn
S

+1
+2
+4
2

2g
1c
1a
4h

0.0
0.5
0.0
0.2552(8)

0.5
0.5
0.0
0.2549(8)

0.5
0.0
0.0
0.2552(2)

1.0
1.0
1.0
1.0

1.46
1.80
0.66
0.86

Atoms

Bond length ()

Atoms

Angle ()

Atoms

Angle ()

CuS

2.333(4)

SCuS

FeS

2.334(4)

SFeS

110.8(1)
107.1(1)
107.5(1)
110.5(1)

CuSFe
CuS-Sn
CuSCu
FeSSn

110.5(1)
108.2(1)
110.8(1)
108.6(1)

SnS

2.397(4)

SSnS

109.4(1)
109.7(1)

FeSCu
SnSCu

110.5(1)
108.2(1)

Intensity [a. u.]

948

P4
20

40
2 [degrees]

60

Fig. 1. Experimental (dotted line) and calculated (solid line) X-ray powder
diffraction patterns of Cu2 FeSnS4 and their difference. The calculated pattern was
obtained from the tetragonal P4 crystal structure reported in [11].

profile fitting, thirteen Raman lines are observed. The spectrum is

characterized by the strongest line at 321 cm1 , three prominent
lines at 218, 284 and 400 cm1 , and several weak spectral
features. These lines are also listed in Table 4. Since the totally
symmetric A modes are expected to be the stronger ones in
the Raman spectra of stannite Cu2 BII CIV XVI
4 compounds [15], the
four strongest lines observed could be assigned to the four A
modes of this compound. As no data on Raman or IR spectra
of P4-Cu2 FeSnS4 appear in the literature, the present data are

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C. Rincn et al. / Solid State Communications 151 (2011) 947951

949

Table 3
Factor group analysis for the zone-center vibrational modes of the tetragonal
(P4)-Cu2 FeSnS4 , z = 1.
Atom

Number of equivalent positions in

Wyckoff notation

Irreducible
representations of modes

Cu
Fe
Sn
S

2 (g )
1 (c )
1 (a )
4 (h)

A + B + 2E1 + 2E2
B + E1 + E2
B + E1 + E2
3A + 3B + 3E1 + 3E2

Raman : 4A + 5B + 6E1 + 6E2 .

IR : 5B + 6E1 + 6E2 .
acoustic : B + E1 + E2 .

Fig. 3. Raman spectrum of tetragonal P4-Cu2 FeSnS4 (O). The full line is obtained
by using a multi-Lorentzian profile fitting. A separate contribution to each peak in
the fitting is shown by dotted lines. The frequencies of all the modes thus obtained
are indicated in the figure. These values and assignments of the A-symmetry Raman
modes are given in Table 4.

Fig. 2. Differential thermal analysis of a typical P4-Cu2 FeSnS4 sample as obtained

from the cooling curve. The temperature of the solidsolid phase transition and the
melting point of the compound were found to be 701 C and 831 C, respectively.
Table 4
Frequency of optical modes (in cm1 ) of P4-Cu2 FeSnS4 observed by Raman
scattering and, whenever possible, its tentative symmetry assignments. For
comparison, frequencies of optical modes for I42m-Cu2 FeSnS4 reported in Ref. [15]
from Far-infrared (IR) and Raman spectra are also listed.
No.

P4-Cu2 FeSnS4

I42m-Cu2 FeSnS4

Experimental

Calculated

Ref. [15]

98

175
224

283

322

412

75 (IR)
96 (IR)
144 (IR)
152 (IR)

7
8
9
10
11
12

96
144

168
218 (A-symm.)
245
284 (A-symm.)

321 (A-symm.)
341
400 (A-symm.)
440
492

13

520

522

1
2

3
4
5
6

286 (Raman)
302 (IR)
315 (IR)
318 (Raman)
344 (IR)350 (Raman)

compared with the reported [15] IR and Raman lines of stanniteCu2 FeSnS4 listed in Table 4. The main difference between these
lines and those obtained here is that our strongest peak is shifted to
a higher frequency (321 cm1 ) as compared to the one observed in
I42m-Cu2 FeSnS4 (318 cm1 ). This slight difference probably arises
from the difference in the cationanion bond distances observed
in these two structures. If can be assumed, as will be discussed
later, that the strongest A-symmetry vibration at 321 cm1 is

Fig. 4. Inverse of the magnetic susceptibility vs. T for P4-Cu2 FeSnS4 carried out on
zero field cooling (H) and on field cooling (). Inset: the variation of the magnetic
susceptibility vs. T for P4-Cu2 FeSnS4 carried out on zero field cooling (H) and on
field cooling ().

a pure anion mode of the S atom around the Sn metal [15], it

frequency can be estimated by the expression v A (SnS /mS )1/2 ,
with mS and SnS being the sulphur mass and the SnS bondstretching force constant, respectively. So that, by supposing that
the empirical model [16] for ternary chalcopyrite compounds
relating the anioncation bond-stretching force constants to the
anioncation bond-distances is valid for Cu2 FeSnS4 , a dependence
5/2
of the form SnS 1/dSnS is expected. Hence, the relation v A
5/2

5/4

(dSnS /mS )1/2 1/dSnS can be used to compare the frequency

of the strongest A mode in stannite- and P4-Cu2 FeSnS4 . Thus,
using dSnS = 2.411(2) for stannite-Cu2 FeSnS4 [7] and dSnS =
2.397(4) for the P4-Cu2 FeSnS4 (see Table 1) we then estimate,
from v A = 318 cm1 for stannite Cu2 FeSnS4 [15], v A 321 cm1
for P4-Cu2 FeSnS4 which coincides with the present experimental
value.

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C. Rincn et al. / Solid State Communications 151 (2011) 947951

3.2.1. Estimation of the Raman mode frequencies in P4-Cu2 FeSnS 4

If the strongest Raman line observed in P4-Cu2 FeSnS4 corresponds to the A-symmetry mode, which originates from the motion of the S anions around fixed Sn cations, its frequency can then
be estimated by using a simplified version of Keatings model [17]
for AI BIII C2VI chalcopyrite compounds based on the approximation that the vibrational frequencies in these compounds depend mainly on bond-stretching forces between nearest-neighbor
atoms. According to this model, the vibration frequency of this A
mode can be estimated by the expression v A (4SnS /mS )1/2 .
Here SnS can be calculated from the above mentioned model
for ternary chalcopyrite compounds [16] relating the cationanion
bond-stretching forces to the cationanion bond-distances. Thus,
for P4-Cu2 FeSnS4 SnS was found to be 49 N/m from the value
of dSnS given in Table 2. v A was then calculated to be 322 cm1 .
Also, SnS and v A for stannite-Cu2 FeSnS4 , calculated in the same
way, yield the values 48 N/m and 319 cm1 , respectively. All
these results are in very good agreement with experimental values for the frequency of the strong Raman line in both P4- and
stannite-Cu2 FeSnS4 which confirm that the strongest Raman Asymmetry mode in Cu2 FeSnS4 can be looked at as a vibration of
S anions around Sn cations. The second strongest Raman line for
P4-Cu2 FeSnS4 can be considered as a pure anion mode around
the Cu cation. This is because a good agreement with this experimental phonon frequency at 284 cm1 is obtained by using
v A (4CuS /mS )1/2 where CuS 38 N/m is the CuS bondstretching force constant, which gives v A 283 cm1 . On the
other hand, in AI BIII C2VI ternary compounds [18] the frequency
of the highest-energy A mode determined from the strength of
the BIII C VI bond is always above about 50 cml than that of
the sphalerite-like mode in the analog AII BVI binary compound.
Hence, in analogy to that observed in these ternaries, it is expected that the corresponding Raman line frequency in Cu2 FeSnS4
could show the same behavior as compared to the corresponding
frequency in it binary analogue ZnS. Thus, the frequency of the
highest-energy A mode in Cu2 FeSnS4 can be estimated by the expression [17] v [4FeS /(1/mFe + 1/mS )]1/2 . This yields, using FeS 51 N/m as the FeS bond-stretching force constant,
the value v 412 cm1 which is in good agreement with the
Raman line at 400 cm1 . This line is also about 50 cm1 higher
than the frequency (v 352 cm1 ) of the transversal optical
mode in ZnS [19]. The other Raman modes observed could be originated from the combined motion of anions and cations. Thus, for
example, the frequency of the mode which resembles the motion
of Fe and Sn ions in phase, as estimated by the expression [20]
v [(FeS +SnS )/(mFe + mSn )]1/2 , is 98 cm1 in good agreement
with the line at 96 cm1 . Moreover, the frequency of the mode
which involves the motion of the Cu and Fe in antiphase, as calculated by the expression v [(CuS + FeS )(1/mCu + 1/mFe )]1/2 ,
is 224 cm1 in good agreement with the line at 218 cm1 . On the
other hand, the frequency of the mode that resembles the motion
of S an Cu in antiphase is given by v [CuS (1/mS + 1/mCu )]1/2 .
This yields v 175 cm1 in reasonable good agreement with
the weak line at 168 cm1 . Finally, the highest-frequency mode
expected to be observed in Cu2 FeSnS4 from the tetra-atomic linear chain model [21] is 522 cm1 as estimated from the expression v [(Cus + FeS /2 + SnS /2)(2/mCu 1/mFe + 1/mSn +
4/mS )]1/2 . This is also in good agreement with the line observed
at 520 cm1 . All the phonon modes observed in the present work
and their tentative symmetry assignments are summarized in
Table 4.

shown in Fig. 4. As observed, for T > 50 K the curve is linear

and its extrapolation to 1/ = 0 gives a negative value of
the CurieWeiss temperature = 74 K indicating that this
compound is antiferromagnetic. Also, as can be seen in the inset
of Fig. 4 where the temperature dependence of is shown, above
15 K same values of are obtained on ZFC (heating run) and
on FC (cooling run) curves indicating that no hysteresis occurs
in this temperature range. It is also seen in the inset that the
antiferromagnetic transition happens at a Nel temperature TN =
38 K. These results show that the present samples have a high
degree of crystallographic order so that spin-glass behavior is
ruled out here. However, as can be seen in Fig. 4, hysteresis of
occurs below 15 K which suggests that at very low temperatures
magnetic anisotropic effects would be important to influence the
spin directions when the applied field is zero or small. On the other
hand, for antiferromagnetic behavior, the variation of 1/ with T
above TN is given by the relation [22] 1/ = (T )/C , where
C is the Curie constant. Thus, from the slop of the straight line in
Fig. 4 and using = 74 K, the value C = 7.1 103 emu K/g
was obtained. This is in excellent agreement with the theoretical
value C = 7.0 103 emu K/g estimated from the expression [22]
C = NA g 2 2B J (J + 1)/3KB W , where NA is the Avogadro number, B
the Bohr magneton, g is the antiferromagnetic coupling constant
and W the molecular weight of the compound. For the calculation
the spin-only parameter values J = S = 2, L = 0 and g =
2 for the Fe2+ ion were used. These results confirm that the
Fe+2 ions are on the 1c sites of the P4 structure giving a typical
ideal antiferromagnetic configuration and no traces of secondary
magnetic phases are present in our samples. Analysis of vs. T for
stannite-Cu2 FnSnS4 has also been reported by other authors [1,2].
For synthetic samples they found 82 and 63 K; C 7.2
and 7.0 103 emu K/g, respectively. These results are in good
agreement with those obtained in the present work.

3.3. Magnetic susceptibility of P4-Cu2 FeSnS4

References

The variation of the inverse of the magnetic susceptibility

1/ with temperature T for a typical P4-Cu2 FeSnS4 sample is

4. Conclusions
The present study performed on synthesized Cu2 FeSnS4 samples indicates that at room temperature this compound crystal However,
lizes in a tetragonal structure with space group P 4.
Cu2 FeSnS4 obtained at temperatures higher than about 700 C,
which are rapidly cooled to room temperature, may retain the
high-temperature -stannite phase and crystallizes in this structure. Hence, a careful process of crystal growth of this material,
including annealing at adequate temperature and slow cooling
of the samples, is necessary in order to obtain specimens with
the low energy P 4 structure. From the Raman scattering spectrum the main Raman lines are observed and its possible symmetry assignments are presented. The frequencies of the A-symmetry
modes estimated by using a simplified theoretical model were
found to be in good agreement with the present experimental data.
From the magnetic susceptibility measurements it was found that
2 FeSnS4 behaves as an ideal CurieWeiss antiferromagnetic
P 4-Cu
material.
Acknowledgments
The authors are grateful to Dr. A.E. Mora and Mr. J.L. Fernandez
for their assistance in the chemical analysis. Financial support
from CDCHT-ULA (C-1436-06-05-AA and C-1438-06-05-Ed) and
FONACIT (grant No. 200900476) are acknowledged. M.A. Macas
would like to thank COLCIENCIAS for his Ph.D. fellowship.

[1] U. Ganiel, E. Hermon, S. Shtrikman, J. Phys. Chem. Solids 33 (1972) 1873.

[2] G.P. Bernardini, D. Borrini, A. Caneschi, F. Di Benedetto, D. Gatteschi, S. Ristori,
M. Romanelli, Phys. Chem. Miner. 27 (2000) 453.

Author's personal copy

C. Rincn et al. / Solid State Communications 151 (2011) 947951

[3] A. Caneschi, C. Cipriani, F. Di Benedetto, R. Sessoli, Phys. Chem. Miner. 31
(2004) 190.
[4] S.A. Kissin, Can. Min. 27 (1989) 689.
[5] P. Bonazzi, L. Bindi, G.P. Bernardini, S. Menchetti, Can. Min. 41 (2003) 639.
[6] L.O. Brockway, Z. Krist. 89 (1934) 434.
[7] S.R. Hall, J.T. Szymanski, J.M. Stewart, Can. Min. 16 (1978) 131.
[8] T.L. Evstigneeva, Y.K. Kabalov, Crystallogr. Rep. 46 (2001) 368.
[9] C. Pietzsch, E. Fritzsch, Chem. Erde 43 (1984) 117.
[10] G. McCarthy, ICDD Powder Diffraction File No. 00-044-1476, 1992.
[11] J. Llanos, M. Tapia, C. Mujica, J. Oro-Sole, P. Gomez-Romero, Bol. Soc. Chil. Quim.
45 (2000) 605. ICDD powder diffraction file No. 01-070-4373. Ref:.
[12] J.C. Woolley, R. Brun del Re, M. Quintero, Phys. Status Solidi A 159 (1997) 361.
[13] D. Caldera, M. Morocoima, M. Quintero, C. Rincn, R. Casanova, P. Grima, Solid
State Commun. 151 (2011) 212.

951

[14] E. Quintero, M. Quintero, E. Moreno, L. Lara, M. Morocoima, F. Pineda, P. Grima,

R. Tovar, P. Bocaranda, J.A. Henao, M.A. Macas, J. Phys. Chem. Solids 71 (2010)
993.
[15] M. Himmrich, H. Haeuseler, Spectrochim. Acta A 47 (1991) 933.
[16] A.S. Verma, Solid State Commun. 149 (2009) 1236.
[17] H. Neumann, Helv. Phys. Acta 58 (1995) 337.
[18] V. Riede, N. Sharif, H. Neumann, H. Sobotta, M.S. Omar, B.R. Pamplin, Cryst. Res.
Technol. 22 (1987) 1089.
[19] W.G. Nilsen, Phys. Rev. 182 (1969) 838.
[20] J.P. Van der Ziel, A.E. Meixner, H.M. Kasper, J.A. Ditzenberger, Phys. Rev. B 9
(1974) 4286.
[21] G.D. Holah, A.A. Schenk, S. Perkowitz, Phys. Rev. B 23 (1981) 6288.
[22] J.S. Smart, Effective Field Theory of Magnetism, Saunders Company, Philadelphia and London, 1966.