Lithium niobates

There is often a wide range of crystalline soHd solubiUty between end-member compositions. Additionally the ferroelectric and antiferroelectric Curie temperatures and consequent properties appear to mutate continuously with fractional cation substitution. Thus the perovskite system has a variety of extremely usehil properties. Other oxygen octahedra stmcture ferroelectrics such as lithium niobate [12031 -63-9] LiNbO, lithium tantalate [12031 -66-2] LiTaO, the tungsten bron2e stmctures, bismuth oxide layer stmctures, pyrochlore stmctures, and order—disorder-type ferroelectrics are well discussed elsewhere (4,12,22,23). 

Only certain types of crystalline materials can exhibit second harmonic generation (61). Because of symmetry considerations, the coefficient must be identically equal to zero in any material having a center of symmetry. Thus the only candidates for second harmonic generation are materials that lack a center of symmetry. Some common materials which are used in nonlinear optics include barium sodium niobate [12323-03-4] Ba2NaNb O lithium niobate [12031 -63-9] LiNbO potassium titanyl phosphate [12690-20-9], KTiOPO beta-barium borate [13701 -59-2], p-BaB204 and lithium triborate... 

Lithium Niobate. Lithium niobate [12031 -64-9], LiNbO, is normally formed by reaction of lithium hydroxide and niobium oxide. The salt has important uses in switches for optical fiber communication systems and is the material of choice in many electrooptic appHcations including waveguide modulators and sound acoustic wave devices. Crystals of lithium niobate ate usually grown by the Czochralski method foUowed by infiltration of wafers by metal vapor to adjust the index of refraction. 

Lithium niobate [12031 -63-9] Nb20 or LiNbO, is prepared by the soHd-state reaction of lithium carbonate with niobium pentoxide. After... 

Of all the piezoelectric crystals that are available for use as shock-wave transducers, the two that have received the most attention are x-cut quartz and lithium-niobate crystals (Graham and Reed, 1978). They are the most accurately characterized stress-wave transducers available for stresses up to 4 GPa and 1.8 GPa, respectively, and they are widely used within their stress ranges. They are relatively simple, accurate gauges which require a minimum of data analysis to arrive at the observed pressure history. They are used in a thick gauge mode, in which the shock wave coming through the specimen is... 

The relatively simple study of fluorescence and phosphorescence (based on the action of colour centres) has nowadays extended to nonlinear optical crystals, in which the refractive index is sensitive to the light intensity or (in the photorefractive variety (Agullo-Lopez 1994) also to its spatial variation) a range of crystals, the stereotype of which is lithium niobate, is now used. 

The contribution to the stress from electromechanical coupling is readily estimated from the constitutive relation [Eq. (4.2)]. Under conditions of uniaxial strain and field, and for an open circuit, we find that the elastic stiffness is increased by the multiplying factor (1 -i- K ) where the square of the electromechanical coupling factor for uniaxial strain, is a measure of the stiffening effect of the electric field. Values of for various materials are for x-cut quartz, 0.0008, for z-cut lithium niobate, 0.055 for y-cut lithium niobate, 0.074 for barium titanate ceramic, 0.5 and for PZT-5H ceramic, 0.75. These examples show that electromechanical coupling effects can be expected to vary from barely detectable to quite substantial. 

The piezoelectric behavior of both quartz and lithium niobate has been studied in a series of careful, systematic investigations. (See Graham and coworkers [65G01, 70101, 75G04].) The experimental arrangement is shown Fig. 4.2. The impactor, preferably the same material as the piezoelectric sample (but perhaps another standard material), is accelerated to a preselected... 

Fig. 4.2. The technique used to study the piezoelectric behavior of the crystals quartz and lithium niobate used controlled, precise impact loading. The impact velocity can be measured to an accuracy of 0.1%, leading to the most precisely known condition in shock-compression science (after Davison and Graham [79D01]).

Typical current pulses observed for x-cut quartz, z-cut lithium niobate, and y-cut lithium niobate are shown in Fig. 4.3. Following a sharp rise in current to an initial value (the initial rise time is due to tilt, misalignment of the impacting surfaces), the wave shapes show either modest increases in current during the wave transit time for quartz and z-cut lithium niobate... 

Fig. 4.3. Typical normalized piezoelectric current-versus-time responses are compared for x-cut quartz, z-cut lithium niobate, and y-cut lithium niobate. The y-cut response is distorted in time due to propagation of both longitudinal and shear components. In the other crystals, the increases of current in time can be described with finite strain, dielectric constant change, and electromechanical coupling as predicted by theory (after Davison and Graham [79D01]).

Fig. 4.4. The piezoelectric charge produced by elastic strain in x-cut quartz and z-cut lithium niobate is well represented by a quadratic relationship without a need for fourth-order contributions.

The measured relationships between piezoelectric polarization and strain for x-cut quartz and z-cut lithium niobate are found to be well fit by a quadratic relation as shown in Fig. 4.4. In both materials a significant nonlinear piezoelectric effect is indicated. The effect in lithium niobate is particularly notable because the measurements are limited to much smaller strains than those to which quartz can be subjected. The quadratic polynomial fits are used to determine the second- and third-order piezoelectric constants and are summarized in Table 4.1. Elastic constants determined in these investigations were shown in Chap. 2. 

Table 4.2. Calibration factors for quartz and lithium niobate gauges.

Lithium niobate is strongly ferroelectric, yet the material behavior under elastic shock loading is apparently fully described by nonlinear piezoelec-... 

Fig. 4.5. The degree of approximation for the increase of current in time for uncoupled and weakly coupled solutions for impact-loaded, x-cut quartz and z-cut lithium niobate is shown by comparison to the numerically predicted, fully coupled case. In the figure, the initial current is set to the value of 1.0 at the measured value (after Davison and Graham [79D01]).

The determination of piezoelectric constants from current pulses is based on interpretation of wave shapes in the weak-coupling approximation. It is of interest to use the wave shapes to evaluate the degree of approximation involved in the various models of piezoelectric response. Such an evaluation is shown in Fig. 4.5, in which normalized current-time wave forms calculated from various models are shown for x-cut quartz and z-cut lithium niobate. In both cases the differences between the fully coupled and weakly coupled solutions are observed to be about 1%, which is within the accuracy limits of the calculations. Hence, for both quartz and lithium niobate, weakly coupled solutions appear adequate for interpretation of observed current-time waveforms. On the other hand, the adequacy of the uncoupled solution is significantly different for the two materials. For x-cut quartz the maximum error of about 1%-1.5% for the nonlinear-uncoupled solution is suitable for all but the most precise interpretation. For z-cut lithium niobate the maximum error of about 8% for the nonlinear-uncoupled solution is greater than that considered acceptable for most cases. The linear-uncoupled solution is seriously in error in each case as it neglects both strain and coupling. 

It appears that the observed breakdown must be explained in terms of the transient behavior of stress-induced defects even though the stresses are well within the nominal elastic range. In lithium niobate [77G06] and aluminum oxide [68G05] the extent of the breakdown appears to be strongly influenced by residual strains. In the vicinity of the threshold stress, dielectric relaxation associated with defects may have a significant effect on current observed in the short interval preceding breakdown. 

The piezoelectric constant studies are perhaps the most unique of the shock studies in the elastic range. The various investigations on quartz and lithium niobate represent perhaps the most detailed investigation ever conducted on shock-compressed matter. The direct measurement of the piezoelectric polarization at large strain has resulted in perhaps the most precise determinations of the linear constants for quartz and lithium niobate by any technique. The direct nature of the shock measurements is in sharp contrast to the ultrasonic studies in which the piezoelectric constants are determined indirectly as changes in wavespeed for various electrical boundary conditions. 

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