j~iirri,iIH (rv,t:il (diisi tli 49 (I950) 334 342

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(JROWTI-I DEFECTS IN ISOMORPHOUS Ba(N0
3)2 AND Sr(N03)2 CRYSTALS
M. RIBET and J.L. RIBET
(~roi1J)i~JeI)inainiqtic c/es P/iascs (oiideiisies (T.STL, lIace 1: . Bata,lloo, 1-34060 Slontpellur (edex, /rancc
:uid
F, LEFAUCHEUX andM.C. ROBERT
Iahorato,re de llineralog,e (ristallograp/iie, Universit Paris VI, 4 Place ,Jussieu, 1-- 75230 Paris Cedex 05, Prance
Received 5 September 979: icanuscript received in final turin 4 December 1979
Crosstli detects in two solut on gros~n,isomorphous crystals of Sr(NO3)2 and Ba)NO3)2 are studied by X-ray topinzr:ipliv.
I . Introduction
Cotta
X-ray topography has clearly shown that growth ,
defects on the who]e can he related to growth condi- t),,
tions. but that some of them can be induced by a par- (it I)
ticular crystal structure. So it was interesting to corn-
pare crystal defects in two crystals of the same series, , I
such as Ba(N03)2 and Sr(N03)2, which belong to the I It) (itt)
family of cubic nitrates of the alkali earth metals.
iii\\
(ill)
2. Experimental conditions
a
The two crystals of Ba(N03)2 and Sr(N03 )2 are
grown on seeds from their water solutions by a slow
temperature decrease method in the temperature 1
range 50-- 30Cwithout stirring; so the whole experi-
tnent is performed at a temperature higher titan
29.3C,which limits the domain of stability of anhy- iii - iii
drous Sr(N03)2. At the beginning of the crystallii.a-
loon process, tite cooling rate is 0.05C/day,tlten it -
is increased to 0.2C/dayat the end of the growth
The as-grown crystals display a cubic habit with ii lii
isometric ~I00} and ~l 11 } faces (fig. 1 a); Ba(NO3)2 t
presents small ~2l0~ faces in addition. b
For X-ray topographs, fi l0} and flOO} plates are lig, I. (a) Habit of Sr)N03)2 and Ba(N03)2 crystals. Posi-
cut and polished (fig. 1 b); the high absorption coeffi- tion of a (ITO) slice used for X-ray studies. b) View of
cient, p, does not allowone to use slices much thicker growth sectors which can be intercepted in such a slice,
334
M Ribet eta!. / Growth defects in isornorphous Ba (NO3)2 and Sr(N0
3)2 crystals 335
than 1 mm: ~i is then ofthe order of 6/mmfor AgK~
and 11/mmfor MoKct (for Sr(N03)2. Topographs of _____
such crystals are complicated further by the fluores-
cence of Sr, excited for X <0.90 A andby the radia-
tion damage, as seen in fig. 7a (lines R). The line R
indicates the position ofan earlier section topograph;
this defect is not optically visible but it presents in
topography a white black contrast, and it can be
removedby chemical etching.
3. Point symmetry
There exists no agreement between different
authors concerning the correct point symmetry of
these crystals. X-ray [2,3] and neutron [4,5] diffrac-
tion studies assigned the space group Pa3: the pres-
ence of a centre of inversion leads to planar NO3
groups. New neutron diffraction experiments [6]
revealed faint reflections which are forbidden in a
Pa3 group: the space groupwould be P213 withtwo
different NO3 groups which build two flattened
pyramids. Numerous Raman and IR studies [717]
could not help to decide between these two hypoth-
eses. Lately, very sensitive measurements [18] could
detect no pie~oelectric,linear electrooptic and non-
linear optic effect, which would be present in space
groupP213.
So etch pit experiments were performed on the
octahedral faces with the etchant proposed by Rao
[19]; their orientations (fig. 2) were different on
(111) and (III) faces, in agreement with Wulffs - -E
observations [20] presented in fig. 2b. The octa-
hedral faces are of two types according to the sense
of rotation of these figures: . The fi1 1} faces
correspond to +e and the {1 I l} faces to -c. Fur-
thermore, in our growth experiments spontaneous
nucleations often present a tetrahedral habit. Growth
from spheres [21] leads to the same conclusion:
absence of a centre of symmetry. Thus, if the mor- b
phological observations confirm the space group
P213, the deviation in comparison toa centred struc-
ture must be faint and could not be detected by phys- Fig. 2. (a) Etch pits on (Ill) and (111) faces ofa Sr(N03)2
ical measurements, crystal. (b) Scheme of etch pits on octahedral faces (after
Wulff 1201.
4. Growth defects observed in Sr(N03)2
ent samples show the same type of defect: disloca-
The growth defects were studied by X-ray topog- tions (d) starting from the seed (S), growth bands
raphy using the Lang method [22]. Slices of differ- (b), strains at the boundaries between two growth
336 M. Rthrt ci al. / Grant/i defects in isomorphaus Ba(iVO
3)2 and Sr(N03)5 eri~ils
sectors (1) and some particular defects (f) which will
be discussedlater.
The spontaneously nucleated crystals (fig. 3) are
fairly good, showing mainly inclusion lines (I) and
sonic strained areas (A); when they are 2 or 3 mni
large, they are used as seeds. If the solution is under-
saturated at the introduction of the seed, it is partly
dissolved (fig. 4) and the beginning of growth is
nearly perfect. On the contrary, if the solution is
slightly supersaturated, a sudden precipitation can ___________________________________________________
deposit small particles on the seed but only on the
exposed faces: these inclusions (I) are sources of dis-
locations as seen in fig. 5, only the sheltered sector
growing downward is dislocation-free.
Most of the dislocations starting from the seed
(fig. 5) are visible as straight lines (d1) normal to the
growth front, were identified as edge dislocations.
Some of them (d2), which belong to the octahedral ________ -
sector, are attracted by the growth sectors bound-
ary and propagate nearly parallel to the growth front.
Nevertheless, one dislocation (d3), trapped in this
boundary is suddenly refracted to the cubic sector.
Some oscillating dislocations (d4), visible in this see- lip. 4. lopograpli of a( 110) slice cut out of Sri NO3 )2 crys-
tor have a strong screwcomponent. tal 11; pd = 9; MoKa; Ill reflection,
The grout/i sectors boundaries show different
contrasts according to the nature of the limit (fig. 6): lies nearly perpendicular to the reflector plane (13).
(i) The boundaries between cubic and octahedral see- For these two cases, this contrast has a dynamical
tors are always visible; they are seenas white or black origin since it reverses from a g to -g reflection
lines (li). When they are inclined on the slice, they (figs. 6b and 6c). Similar observations of growth see-
give fringes (12) only visible near the entrance and exit (or boundaries in quartz [23,24] and in KDP [25,
surfaces: this boundary becomes out of contrast if it 26] have been already reported. These authors have
Fig, 3. Topograph 01 :1 0 ItO slIce i_ut out Iii spontaneou4~ nuelc.i ted Sr(N03)2 c~~t~l I; MoKo: 111 reflection.
M. Ribet era!. /Growth defects in isomorphous Ba(NO3)2 and Sr(NO
3)2 crystals 337
growth bands are never seenin the octahedral sectors.
As segregations of impurities induce lattice niisorien-
ft Pb(N03)2 and Ba(N03)2 [27]; when the gro~his
-! performed with addition of methylene blue ofagiven
_______________ concentration, this impurity is incorporated either in
- ~LJ . -
- cubic sectors [Pb(N03)2] or in octahedral sectors
[Ba(N03)2].
In addition to these defects which are well known
.~ to occur in solution grown crystals, some other par-
ticular defects (f) are also present in these crystals,
but only in the cubic sectors. They are seen differ-
\ ently according to the orientation of the slice. On a
~ -[1 10} plate (fig. 6a), first, little short lines (f1)
nearly perpendicular to the growth front are seen in
the two cubic sectors whose normal lies in the plane
- of the slice- secondly long lines (f2) nearly parallel
1-ig, 5. Topograph of a (1 1 0) slice cut out of Sr(N03)2 crys-
tal III; pci = 9: MoKcs; 111 reflection, to the growth front cross the other two cubic sec-
tors. These two defects present similar orientation
and contrast in a section topograph but the direc-
made double crystal reflection topographs and con- tion of the fault cannot be determined on account
eluded that the bending of the crystal planes is due of the high absorption of Sr(N03)2. For a flOO}
to a difference in the lattice parameters on either plate, the normals of all cubic sectors lie in the plane
side of the boundary. Measurements on Sr(N03)2 are of the slice, so only the short lines (f1) can be seen
now in progress by means of a double crystal spec- (fig. 8a) but, as their contrast is often very weak,
trometer in order to decide on the nature of the only growth bands can be visible (fig. 7b). As for the
strain, contrast, the reflection 200 shows a good extinc-
(ii) The boundaries between two cubic or two octa- tion for these two fdefects (fig. 9a), which are clearly
hedral sectors are very difficult to see: when they visible on the 1 I1 reflection, so the fault vector is
exist, they often trap dislocations (d in figs. 7a and perpendicular to the defect. The image of this defect
7b); nevertheless, the strain must be much weaker has a dynamical origin because the spacing of the
in these boundaries than in the preceding case: no lines (f1 or f2) varies with the order of reflection (figs.
contrast is seen fromA to B (fig. 7). 9b and 9c). For moire-like fringes, the fringe spacing
Growth bands (b) parallel to the growth front are is inversely proportional to the order of the reflec-
visible only if they are normal to the slice. For exam- tion; for planar defects, the fringe spacing varies as
ple (fig. 8a), such defects have a strong contrast in the the extinction distances. In our case, the observed
(001), (001) and (100) sectors but cannot be seenin fringe spacings for 111, 222 and 333 reflections are
the (010) sector which is parallel to the slice. Since respectively proportional to 1, 0.5 and 1: that is the
they are out of contrast in the (001) and(001) see- same variation for the extinction distances which are
tors for the 200 reflections (fig. 8b), their fault vec- respectively 81, 47 and 104 jim. Thus these defects
tor is perpendicular to the plane of the fault; such are really faults whose orientation is not yet deter-
defects are usually explained by the segregation of mined. However the f-defects are difficult to inter-
impurities on the growth front inducing a fault per- pret because they are numerous and the associated
pendicular to the growth face. On the contrary, such strain field must be very weak. The direction of the
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M. Ribet era!. / Growth defects in isomorphous Ba(N0
3)2 and Sr(N03)2 crystals 339
(11,)
a
b
Fig. 7. (a) Topograph of a (110) slice cut out of Sr(N03)2 crystal IV; pd = 7; MoK~111 reflection. (b) Topograph nfa (001)
slice cut out of Sr(N03)2 crystal III; pd = 7; MoKo; 111 reflection.
f1 defects show that lattice distortions exist be- or {4, 1, 0} for Pb(N03)2. The cube faces are
tween different parts grown from the same cubic built up of an oscillatory repetition of such faces.
growth front. So, these defects can be considered In consequence, successive subsectors boundaries
as lineages, a name proposedby Buerger [28] for between (kOl) and (kOi) faces could be expected.
all such grains whose orientations descend contin- The same mechanism which is clearly visible with
uoushy from the same parent nucleus but whose large dye molecules could be realized on a small
mutual orientation may differ. The term lineages scale with atoms like Ba for Sr(N03)2 crystals, Ba
can cover defects fromvarious origins [29,30] such being the major impurity in that case. In order to
as subsectors, growth twins, segregation of impuri- verify this hypothesis, growths from mother liquid
ties leading even to intergrowth of different species containing various amounts of Ba are to be per-
like quartz in feldspar crystals [311.In our case, a formed. A completely different explanation for these
review of the literature concerning the series of iso- f-defects is related to the very small deviation from
morphous nitrates shows that none of the possible the centrosymmetry attributed to the NO3 groups.
origins just mentioned can be excluded. Impurities The NO3 groups build flat pyramids [6] with the 0
such as methylene blue [32] are strongly adsorbed atoms in the {11 l} planes: so N atoms could occu-
on the cubic faces, but not homogeneously: the faces py two positions energetically equivalent on each
are striated parallel to the cubic axes. This striation side of the basal plane. It can be understood that
is due to aset ofvicinal faces: {I6, 1, 0} forBa(N03)2 the NO3 groups are better oriented on fill } faces
340 51. Ri/tel ci a!. / Grant/i defects in isaniorphaus BaINO
3)2 and Sr(N03)2 cristals
ion
a
(100)
~ -_- ~ 1
lip. 8. Topograph ofa (((It)) slice cut out of Sr(N03)2 crystal EEI:pd = 7; MoKa: (a) III reflection: (Ii) 200 reflection
than on f100} faces; orderdisorder phenomena graph is due to numerous surface defects created by
should be sensitive to temperature rises there, but polishing which is niore difficult for Ba(N03)2 than
X-ray topographs at 185Cshowno modification of for Sr(N03)2. The most striking growth defects are
these defects, inclusion lines (I) along the growth front indicating
than the flux of matter was not sufficient at the end
of the growth; few dislocations (d) start from these
5. Growth defects observed in Ba(N03)~ inclusions or from the seed (not seen on this plate).
But contrary to Sr(N03)2, whichis grown under sini-
Fig. 10 presents a (110) plate cut out of a ilar conditions, this crystal presents no growth band,
Ba(NO3)2 crystal. The granula aspect of this topo- no strain at the growth sectors boundaries, and no
M. Ribet eta!. / Growth thfccts in isornorphous Ba(NO
3)2 and Sr(N03)2 crystals 341
Fig. 9. Topograph of the same part of a (110) slice cut out ofSr(N03)2 crystal III: (a) AgKn 200 reflection: (b) AgKo 111 reflec-
lion; (c) AgKcs 222 reflection.
f-defect. This fact can be attributed to the size dif- the growth front leads to growth bands; on the con-
ference of the two ions: Sr
2~andBa2~.In the case of trary, Sr can be incorporated in Ba(N0
3)2 crystals
Sr(N03)2, the mother solutions always contain Ba without large lattice distorsion. Growth experiments
as a major impurity which cannot be incorporated with Ba-free solutions of Sr(N03)2 are now in prog-
without lattice deformation, so its segregation along ress in order to verify this hypothesis.
342 11 Ri/ic! ci a! / Growth defects in is0010rp/ioos /la(N0
3)2 and Sr(N03)2 crtstal
References
AN). VergnoLx, .1. (hord:ino and .1.1.. Ribet i ( r~st:il
Growth 1 (1967) 11(1.
2 L. Vegard, Z. Physik 9 (1922)395.
___________________ 13 I ~ Jai~tcr,:~nd ~ v:ii Melle. Proc. Kon. \led.Akad
141 \V. Hamilton, i\cfaCrvst. 10 (1957) 103.
I~IC. Lutz. Z, Krist. 114 (1960) 232.
161 R. liirnstock, 7.. Krist 124(1967) 310.
_________________ 171 II. (;ross and A. Shultin, Soviet Phys.Doki. 2 (1957)
___________ ______________ 371.
______ 1811). ltloor, Spectrochint, Ada 21)1965)133.
_______ l9I(.Il.J. Schuttc, Z. Krist, 126 (1968)397.
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________ (1970) 1351.
[lIb M.ll. Brooker, l).l . Irish and G.E. Boyd. J. (lieni. lliss
______ 53 (1970) 1083.
1121 Niicliarcl, Zarcnihovifch and \acber, Plionons (1971)
. 113 I M.l I. Brooker and .1. Bates, Spectrochini Ac a 29A
ct. I )(. I opocr~tp1iof a (lift) slice i_Lit alit at :i Ba) NO 1)2
crystal; \loKa: Ill reflection. . (1973) 439.
141 NI. Scrocco and I . Mattioli, Phvs. Status Saudi 072
(1975) Kl3.
1151 A,N1. Ban, C, Bcnoit and 0. Bernard, Phis. Status
In conclusion, the crystalline quality of Ba(NOa)2 Solidi B78 (1976) 67.
- . - 11~ll).V, l.uoi. NI. Abenoza and A. Ariuengaurf, Spectra
is very good, large parts are defect-free either in the cliini Aeti 13c\ (1977) II
cubic sectors, or in the octahedral sectors. 1171 NI Scrocca :ind L, Mattio!i, Ihys. Status Saudi 086
1978) KI.
1181 S. IlaLisslilil, 7.. Krist.. Kristallogeoin. Krista!lpli~s.
6 Conclusion Kristallchieio. 146 (1978)303.
1191 SM. Rail and KG. Bansigir, Indian J. Pure Appl. Pltys.
4(1966) 363.
Isomorphous crystals of Ba(NO3)2 and Sr(N03)2 1201 L. Wolff, Z. Krist. 04 (1880) 1 22.
grown under similar conditions from water solutions 1211 A.V. Belyustin, EM. Levina and 1.1. Novoseltseva,
showstrong differences in crystalline quality. Defects Soviet Phys.-Cryst. 13 (1969) 633.
- , i~iAR I in I A I Phs ~9(1958)597
usually observed tn solution grown crystals such as ~...
- . . 1231 l).Y. Parpia. Plul. NIag. 33(1976) 715.
growth bands or visible growth sector boundaries, can 1241 J.Yoshinitira, I Niivazaki, T. \Vada. K. Kolira, NI
be eliminated for Ba(NO3)2 but not for Sr(NO3)2. llosak:i, T. Oguwu md S. Taki, J. Crystal Growth 46
The difference can he due to some inconvenient (1979) 691.
impurity in the mother solution or to some difference 125 I C. Belouet, I . Dunia and J.l. letroff. 1. ( rystal Growth
in the structure. Furthermore Sr(N05)2 crystals do 230974) 243.
261 C. Belouct :mnd WI. Stacy, J. Crystal Grontlm44 (1978)
not present a homogeneous perfection: only large 11
parts of the octahedral sectors can he defect-free. 1271 1 .N, Slavnav:m, in: Camtfi of Crystals, Rept. (an).
1956) p. II7.
1281 M.i . Bucrgcr, Ani. Mineralogist I 7 (1932) 177.
Acknowledgment 1291 Nl.J. l3uerger. Z. Krisf. 89 (1934) 195. 242
13011. lctreus, Am. Mineralogist 63 (1978) 725.
31 I 1)1. Grimzorev. Ontogeny of NI inerals t Israel lrogr. for
The authors are grateful to Dr. B. Simon for help- Sci. Transl., Jerusalem, 1965).
ful discussions. 132111.1. Buckley, Z. Kristall Mineral. 1176 (1931) 147.