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New Experimental Methods for Perturbation Crystallography.
Heunen, G.W.J.C.
Publication date
2000
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Citation for published version (APA):
Heunen, G. W. J. C. (2000). New Experimental Methods for Perturbation Crystallography.
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Appendixx B
PiezoelectricPiezoelectric Materials Used
Thee developed methods were tested and applied to the following piezoelectric crystals: LiNbO^, KT1OPO4,, AgGaS2, KH2PO4 and KD2P04. A short description of the properties and main physical
interestt is given for each material, followed by a focus on the piezoelectric issue. The crystallographicc data of these materials can be found in Table B-l.
LiNbO.i i
Lithiumm niobate or LiNbCh is a high-quality single-crystal material which is used in many electronicc and electro-optic applications'11. It has a congruent melting point at 1513 K which dependss on the chemical composition'21. Stoichiometric crystals can be obtained by lithium vapour-phasee equilibration at 1373 K131. Furthermore, the physical properties of LiNbO.i also depend on the composition.. For example, the congruent phase has a ferroelectric Curie temperature Tc of 1402 K, whereass the stoichiometric phase has a 7;. of 1471 K|4]. A detailed study of both the congruent and stoichiometricc crystal structures has been presented by Abrahams et al.'"'1'
Fujimoto'6'' determined the piezoelectric tensor elements (rf?/=-0.77-10"12 CN-1 and ^ = 8 . 4 - 1 0 '2
CN"" ), but it is unclear whether the sample was stoichiometric or congruent. Several other studies reportedd values for the piezoelectric constants'7' to be in the range of 6-910 l2 and 16-1910 12 CN"1. Furthermore,, Stahl et al."' showed that the stoichiometric crystals have surface layers that differ in thee r-axis when an electric field is applied.
Itt should be noted that the LiNbOi samples used for this work have a congruent composition. KTiOP04 4
Potassiumm titanyl phosphate or KT1OPO4 (KTP) is a compound with large second-order dielectric constants'*'' and is, because of its low thermal expansion coefficients and the slow variation of its opticall constants with temperature, often used as a second-harmonic generator of near-infrared laserr light'4' and the preferred material for electro-optic applications"01. It is also a quasi
one-dimensionall ionic conductor above 150 K[l1'12' due to the high mobility of the potassium ions. The crystall structure of KTP was first determined by Tordjman et al.|L,] An extensive review of the crystall structure and the physical and chemical properties of KTP has been published by Stucky et al."4',, whereas Thomas et al."'1' reanalysed the structure. A detailed analysis of the electron-density distributionn was carried out by Hansen et al."6 1 7', who discuss the relations between the crystal structuree of KTP, the optical properties and the electron-density distribution from X-ray diffraction data.. On the basis of diffraction experiments at several temperatures between 10 and 1100 Kilx',
studiess on the formation of ferroelectric domains as well as poling experiments, have been carried out119"21'.. In recent years, there has been a growing interest in the technique of periodic domain inversionn (PDI) to achieve quasi-phase-matching (QFM), a procedure to introduce an array of domainss of alternating structural polarity into a polar crystal .
Twoo publications have appeared in which the full piezoelectric tensor is given. However, the two resultss show large discrepancies for almost all the tensor elements. For the piezoelectric constant ,, SiFvestrova et al.124' determined a value of 25.8-10 '2 CN"1, whereas Chu ct al.'2"' report a value off 10.4-10 "12 CN"1. Similar differences are found for d.u and di2, with the value of Chu et al. always beingg lower. Both groups performed the measurements at room temperature and used the direct piezoelectricc effect but, unfortunately, give no indication of the precision of their results.
AgGaS: :
Silverr thiogallate or AgGaSj is a member of the A[BniC2vi family of compounds with a
ehalcopyritee structure. A detailed study on the atomic arrangements was performed by Abrahams et al.|2fl'' Furthermore it shows non-linear optical properties
Abrahamss et al.1291 determined the absolute sense of the piezoelectric constants d]4 and d}b, being bothh positive, by means of the X-ray absorption edge method'101. Graafsma et al. determined both valuess by single-crystal X-ray diffraction (8.8{9)101 2 and 7.6(1.8)10 l2 CN1, respectively). Furthermore,, they found by means of a structural refinement procedure, that the changes in the positionn of Ag agreed to their calculated values whereas the observed shift in Ga was 10 times largerr than the calculated one and had a larger shift than Ag.
KFFPO44 and K D:P 04
Potassiumm dihydrogen phosphate (KDP) exhibits a phase change at low temperatures (123.5 K), weree the tetragonal (142d ) form goes into the ferroelectric orthorhombic (Fdd2) structure'1"1 with a polarr axis along the original tetragonal r-axis. KDP is well known for its non-linear optical properties,, like second-harmonic generation, and has a profound pyroelectric behaviour. The phase transitionn has been theorised["'>41 and studied extensively as function of temperature "'" ' and pressure1 3'4'.. Recently, surface atomic structure studies on KDP in its growth solution are becomingg available' .
Thee piezoelectric constants t/]4 and rf^ at room temperature have been determined by Mason et
al.14111 (1.3-10 '2 and 2 1 1 0 '2 CN"1, respectively) and 30 years later by Zaitseva et al.'42' (4(2)10 12 andd 2 2 ( 1 ) 1 0 l2 CN"', respectively). Both found that the piezoelectric constant d<f> is temperature dependentt and shows a marked anomaly at the phase transition temperature as is shown Figure
B-la.. On the contrary, the dl4 changes by less then a factor of 10 as the temperature approaches the phasee transition point (Fig. B-lb). A study of A///(, effects in KDP upon application of an electric
fieldd (DC) was performed by Trushin et al.141' using X-ray diffraction. They showed that ammonium dihydrogenn phosphate has in general larger A///n values than KDP in a comparative analysis using
;C3 3 ;50 0 2 0 0 0
Temperaturee K
2 5 0 0 3 0 0 0
200 0 T e m p e r a t u r e , ,
FigureFigure B-l: Piezoelectric moduli of KH2P04 as a function of temperature, a: The
dd3636 according to measurements of the direct effect (triangles) and the
converseconverse effect (open circles) (from Bantle and Caflish44 and von Arx and BantleBantle , respectively) and, b: The d,4 (from Ess4''}.
Thee substitution of deuterium for ordinary hydrogen in KDP i.e. KH:.vDitP04 with A > 0 . 9 5 (DKDP)
iss known to cause a remarkably large shift1321 in the Curie point which is 213 K. Sliker and Burlagee found a Tc of 222( 1) K and concluded that the samples used by earlier workers were less
[48-51 1
on n completelyy deuterated. Several studies have been performed on the effects of deuteration
thee crystal structure of KDP and showed that a reversible transition between two phases, tetragonal andd monoclinic. exist. The same temperature dependence of the dif, of DKDP can be observed as for
KDP.. However, at room temperature the dif) of DKDP was determined by Sliker and Burlage14 ' as beingg 58(2)-10, : CN"1, so twice as large as the d^ of KDP.
Itt should be noted that the DKDP samples used in this work are deuterated for 989< and that the crystall is tetragonal.
TableTable B-l: Crystallographic data of used samples at room temperature.
Material l LiNbOj j AgGaS2 2 KH:P04 4 KD2PO4 4 KTOPO4 4 Crystal l class s Hexagonal l Tetragonal l Tetragonal'4*1 1 Tetragonal l Orthorhombic'^' ' Space e group p R3c c I42d d I42d d I42d d Pna2, , aa [A] 5.1505 5 5.75722 2 7.4521(4) ) 7.4690(5) ) 12.814(6) )
MA] ]
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