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. 2021 Jul 5;11(7):1753. doi: 10.3390/nano11071753

Optimizing K0.5Na0.5NbO3 Single Crystal by Engineering Piezoelectric Anisotropy

Weixiong Li 1,, Chunxu Chen 1,, Guangzhong Xie 1, Yuanjie Su 1,*
Editor: Seok Woo Lee1
PMCID: PMC8308187  PMID: 34361139

Abstract

K0.5Na0.5NbO3 is considered as one of the most promising lead-free piezoelectric ceramics in the field of wearable electronics because of its excellent piezoelectric properties and environmental friendliness. In this work, the temperature-dependent longitudinal piezoelectric coefficient d33* was investigated in K0.5Na0.5NbO3 single crystals via the Landau–Ginzburg–Devonshire theory. Results show that the piezoelectric anisotropy varies with the temperature and the maximum of d33max* deviates from the polar direction of the ferroelectric phase. In the tetragonal phase, d33maxt* parallels with cubic polarization direction near the tetragonal-cubic transition region, and then gradually switches toward the nonpolar direction with decreasing temperatures. The maximum of d33o* in the orthorhombic phase reveals a distinct varying trend in different crystal planes. As for the rhombohedral phase, slight fluctuation of the maximum of d33r* was observed and delivered a more stable temperature-dependent maximum d33maxr* and its corresponding angle θmax in comparison with tetragonal and orthorhombic phases. This work not only sheds some light on the temperature-dependent phase transitions, but also paves the way for the optimization of piezoelectric properties in piezoelectric materials and devices.

Keywords: piezoelectric, anisotropy, K0.5Na0.5NbO3, phase, temperature

1. Introduction

With the gradual deepening and prosperity of the smart wearable industry revolution, piezoelectric-based flexible electronics have attracted considerable attention because of their promising applications in robotics [1], human–machine interaction (HMI) [2], energy harvesters [3], and internet of things (IOT) [4]. Lead-based perovskites, such as Pb(ZrxTi1−x)O3 (PZT) [5] and Pb(Mg,Nb)O3 (PMN) [6] ceramics, possess huge piezoelectric properties but cause severe environmental and health concerns owing to their toxicity. As a promising alternative to lead zirconate titanate (PZT), the K0.5Na0.5NbO3, a lead-free ferroelectric material, has exhibited outstanding piezoelectric performance near the polymorphic phase boundary (PPB) [7] and attracted massive attention worldwide in recent years due to its environmental friendliness [8,9,10,11,12,13]. Owing to its unique merits of a high piezoelectric coefficient (d33), excellent ferroelectric properties, and a high Curie temperature (Tc = 420 °C), KNN has been widely utilized in energy-harvesting devices, transducers, actuators, and sensors [14,15,16,17,18,19,20,21]. Although pristine KNN ceramics possess relatively low piezoelectricity (d33~80 pC/N), they can be remarkably improved by tuning sintering conditions [22], domain engineering [23], phase boundary engineering [24,25], texturing [26], and so on. Furthermore, since the intrinsic piezoelectric response is intimately associated with spontaneous polarization rotation, the anisotropy of piezoelectric capability plays a crucial role in the application of piezoelectric materials [27]. Anisotropy of piezoelectric properties had attracted massive attention in the 1980s, and unprecedented large piezoelectric anisotropy was observed in lead titanate ceramics with random grain orientations [28,29]. However, limited works have focused on the piezoelectric anisotropy of K0.5Na0.5NbO3 single crystals.

The main purpose of this work is to study the piezoelectric anisotropy of K0.5Na0.5NbO3 single crystals as a function of temperature and to unravel the impact of phase transitions on the orientation and amplitude of the longitudinal piezoelectric coefficient. Landau–Ginzburg–Devonshire (LGD) theory was utilized to calculate the three-dimensional surface of the longitudinal piezoelectric coefficient d33* for KNN single crystals in three ferroelectric phases as a function of temperature. Temperature-dependent free energy and spontaneous polarization of KNN has also been investigated to interpret the derivation of piezoelectric coefficients stemmed from temperature variation.

2. Materials and Methods

The ferroelectric capabilities of KNN single crystals were systematically investigated through the Landau–Ginzburg–Devonshire (LGD) function. To achieve more convenience in expressing piezoelectric coefficients in light of the coordinate system for each ferroelectric phase, the cubic paraelectric phase was selected as the reference. The thermodynamic potential function G of the KNN single crystal can be written as [30,31]:

G(σ,E,T)=fLGD+felastic+felectric (1)

where the Landau energy density is given by

fLGD=α1(P12+P22+P32)+α11(P14+P24+P34)+α12(P12P22+P12P32+P22P32)+α111(P16+P26+P36)+α112(P12(P24+P34)+P22(P34+P14)+P32(P14+P24))+α123P12P22P32+α1111(P18+P28+P38)+α1122(P14P24+P14P34+P24P34)+α1112(P16(P22+P32)+P26(P32+P12)+P36(P12+P22))+α1123(P14P22P32+P24P32P12+P34P12P22)12s11(σ12+σ22+σ32)s12(σ1σ2+σ1σ3+σ2σ3)12s44(σ42+σ52+σ62)Q11(σ1P12+σ2P22+σ3P32)Q12(σ1(P22+P32)+σ2(P32+P12)+σ3(P12+P22))Q44(σ4P22P33+σ5P1P3+σ6P1P2) (2)

Here, α denotes the Landau coefficients determined under the stress-free condition [28], σi denotes the ith component of stress in Voigt notation, s11, s12, and s44 denote the elastic compliance constants of a cubic phase [29,30,31], and Q11, Q12, and Q44 denote the corresponding electrostrictive coefficients between polarization and stress [32,33].

In this work, PijPc, ηijPc, and dijPc denote the polarization, dielectric susceptibility, and piezoelectric coefficient in the KNN single crystal for each phase, respectively. For studying the orientational dependence of piezoelectric coefficients, Euler angle (φ,θ,ψ) is utilized to quantitatively describe the rotation in terms of ferroelectric phase coordinates.

The Landau coefficients, elastic compliance constants, and electrostrictive coefficients are taken from Jianjun’s previous work [34]. The dielectric constant possesses a positive proportional relationship with relative dielectric stiffness (εijp=1+ηijpηijp). K0.5Na0.5NbO3 endures a series of phase transition (cubic→tetragonal→orthorhombic→rhombohedral) in the process of cooling from the paraelectric phase. The following relations were utilized to calculate the temperature-dependence of piezoelectric coefficients dijp and dielectric susceptibility coefficients ηijp of KNN crystals as a function of spontaneous polarization,

χij=ε02fLGD/PiPj(i,j=1,2,3) (3)
ηij=Aji/Δ(i,j=1,2,3) (4)
gij=2fLGD/Piσj (5)
dij=ε0ηikgkj (6)

where Aji and Δ refer to the cofactor and determinant of the χij matrix.

3. Results and Discussion

The LGD-free energy density fLGD of the tetragonal phase, orthorhombic phase, and rhombohedral phases, respectively, is plotted as a function of polarization at various temperatures, as shown in Figure 1a–c.

Figure 1.

Figure 1

The Calculated LGD-free energy as a function of polarization (Ps) in (a) tetragonal phase, (b) orthorhombic phase, (c) rhombohedral phase at various temperatures.

Figure 2 and Figure 3, respectively, elucidate the calculated dielectric susceptibility coefficients ηijp and piezoelectric coefficients dijp for K0.5Na0.5NbO3 single crystals as a function of temperature in all three ferroelectric phases, respectively.

Figure 2.

Figure 2

Calculated dielectric susceptibility coefficients for K0.5Na0.5NbO3 single crystals as functions of temperature in all three ferroelectric phases.

Figure 3.

Figure 3

Calculated piezoelectric coefficients for K0.5Na0.5NbO3 single crystals as functions of temperature in all three ferroelectric phases.

According to the Landau–Ginsburg–Devonshire theory, the polarization, i.e., the second derivative of thermodynamic potential function G, can be acquired as a function of temperature by minimizing the total free energy in terms of polarization. Figure 4 illustrates the temperature-dependent spontaneous polarization of K0.5Na0.5NbO3 single crystals in the three phases. It can be clearly seen that polarization goes up with the cooling process for all the ferroelectric phases. Sudden rises were observed at the regions of phase transitions, where 648 K for cubic to tetragonal, 469 K for tetragonal to orthorhombic, and 130 K for orthorhombic to rhombohedral, which is consistent with the experimental results of 694 K, 468 K and 125 K, respectively, from Egerton et al. [35]. It is worth noting that the calculated polarization becomes zero when the temperature is approaching Curie temperature, implying that the system switches to paraelectric phase. Figure 5 displays the free energy (ΔG) of K0.5Na0.5NbO3 single crystals in the three phases as a function of temperatures.

Figure 4.

Figure 4

Spontaneous polarization of K0.5Na0.5NbO3 single crystals as a function of temperatures.

Figure 5.

Figure 5

Free energy (ΔG) of K0.5Na0.5NbO3 single crystals in the three phases as a function of temperatures.

The piezoelectric properties are proportional to the flattening of the free energy profile. It can be clearly seen that the tetragonal-cubic phase transition causing an enhanced d33t (Figure 3) can also be explained by the flattening of the free energy profile (Figure 1a). Consequently, the delayering of the free energy profile favors the enhancement of dielectric susceptibility. It is obvious that in the orthorhombic phase, the increasing temperature flattens the LGD-free energy well and makes it shallower with the heating-up process (Figure 1b), giving rise to the increase in dielectric susceptibility, and thus the increase in its piezoelectric response (Figure 1b). As for the temperature-dependent free energy for the rhombohedral phase in Figure 1c, the delayering of the free energy arising from the temperature rising also contributes to the enhancement of piezoelectric coefficients lying along a no-polar direction (Figure 3).

In the tetragonal phase, the value of d33t for K0.5Na0.5NbO3 crystals in the rotated coordinate along an arbitrary direction can be expressed as:

d33t*(θ)=cosθ(d15tsin2θ+d31tsin2θ+d33tcos2θ) (7)

where angle θ denotes rotation always from [100]t. In the tetragonal phase, (P1 = P2 = 0, P3 =P3Tc  0).

Therefore, by using Equation (7), the three-dimensional profile of calculated d33t*(θ) of the tetragonal phase for three selected temperatures 500, 550, and 600 K is displayed in Figure 6a–c, respectively. As the temperature goes down from the cubic phase to the orthorhomibic phase, the surface of d33t*(θ) varies during the cooling process. The direction of the largest d33maxt*(θ) lies along [001]c direction at 600 K then switches to θmax = 32.5° at 550 K, and finally to θmax = 48.6° at 500 K.

Figure 6.

Figure 6

The orientation dependence of piezoelectric coefficient of K0.5Na0.5NbO3 single crystals in the tetragonal phases at the temperature of (a) 500 K, (b) 550 K, (c) 600 K.

Attributed to the expression of d33t*(θ) in Equation (7), it is obvious that d33t*(θ) is determined by three parameters d33t, d31t, and d15t.

As shown in Figure 3, d33t and d15t changes rapidly near the temperature range of tetragonal-cubic and tetragonal-orthorhombic phase transitions, respectively, while little change in d31t was observed in comparison with d33t and d15t. The d15t behaves like the dielectric permittivity (η11t,η22t) in the cubic phase as a function of temperature and increases with the process of cooling down toward the ferroelectric phase. When the temperature rises toward to the cubic phase (Figure 3), d33t surpasses d15t obviously.

As shown in Figure 2, calculated dielectric constants η11t and η33t vary in opposite tendencies in the whole tetragonal phase temperature range, which gives rise to a maximum d33maxt*(θ) along the polar direction in the high-temperature range. As displayed in Figure 7 and Figure 8, the corresponding angle θ for the maximum value of d33t* varies as a function of temperatures, which clearly demonstrates the influence of temperature on the phase transition. It can be seen that the maximum d33maxt*(θ) stays along [001]t at high temperatures but deviates from [001]t to the nonpolar direction when the temperature goes down, near the orthorhombic-tetragonal point. At the temperature T = 450 K, the maximum d33maxt*(θ) = 521.9 pC/N lies along the direction defined by θmax = 52.98°. The maximum d33maxt*(θ) decreases at first, and then rises with increasing temperature, leading to a minimum at 550 K. This is because d15t keeps increasing while d33t*(θ) keeps decreasing during the cooling process, leading to the orientation variation and amplitude change of maximum d33maxt*(θ). It is reported that the pure KNN at 433 K exhibits a piezoelectric coefficient of 108 pC/N [36], which is similar to our calculated results (Figure 7) along the polar direction at 500 K. As shown in Figure 8, the angle θmax for the maximum d33maxt*(θ) in tetragonal K0.5Na0.5NbO3 deviates away from 0° once the temperature is below 560 K. It should be noted that the d33maxt*(θ) of KNbO3 (KNO) single crystals follows a similar tendency as that for the KNN single crystal because they have the same phase transition sequences and structures [37]. As for the PbTiO3 single crystal [38], the maximum d33maxt*(θ) lies along the polar direction at all temperatures because its shear coefficient is too small at all temperatures to rotate d33 away from the polar direction, which is quite different from the change trend for KNN.

Figure 7.

Figure 7

The piezoelectric coefficient in the tetragonal K0.5Na0.5NbO3 as a function of angle θ at various temperatures.

Figure 8.

Figure 8

Maximum of piezoelectric coefficient and its corresponding angle θmax as a function of temperature for the tetragonal K0.5Na0.5NbO3.

In the orthorhombic phase, more complex behaviors were observed in the variation of piezoelectric coefficients as a function of temperature in K0.5Na0.5NbO3 (Figure 3). Compared with d31o, d32o, and d33o that are relatively insensitive to temperature, the two different shear coefficients play a key role in piezoelectricity, where the shear piezoelectric coefficient d15o declines with increasing temperature, while d24o follows an opposite tendency, as shown in Figure 3. As a consequence, the piezoelectric coefficient d33o* in K0.5Na0.5NbO3 exhibits a more sophisticated temperature-dependent trend compared with the tetragonal phase:

d33o*(ϕ,θ)=cosθ[(d15o+d31o)sin2θsin2ϕ+(d24o+d32o)sin2θcos2ϕ+d33ocos2θ)] (8)

For the orthorhombic phase with P1 = 0, P2 =P3=P3Oc  0, the surface of the piezoelectric coefficient at four chosen temperatures of 200 K, 250 K, 300 K, and 350 K are respectively shown in Figure 9a–d. With a decreasing temperature, the direction of the maximum d33o* was slightly changed from the polar direction [001]°. The distinct changing tendencies of d15o and d24o are apparently responsible for the 90° rotation of the direction of the maximum d33o* in the cooling process. For instance, at 200 K, the maximum d33o* of 157.204 pC/N lies along the direction defined by θ = 52.4° and φ = π/2 (Figure 9a), but switches to the direction defined by θ = 52.9° and φ = 0 at 350 K with an amplitude of 291 pC/N (Figure 9d). Note that the d33o* reaches up to 223.87 pC/N at 300 K, which is very closed to the experimental results of 218 pC/N, indicating the accuracy and reliability of our modeling and calculation [39].

Figure 9.

Figure 9

The orientation dependence of piezoelectric coefficient of K0.5Na0.5NbO3 single crystals in the orthorhombic phases at the temperature of (a) 200 K, (b) 250 K, (c) 300 K, (d) 350 K.

As unraveled in Figure 10, Figure 11, Figure 12 and Figure 13, the temperature-dependent maximum d33maxo* and its corresponding angle θmax are illustrated in planes of φ = 0 and φ = π/2 to systematically indicate the piezoelectric anisotropy of the orthorhombic K0.5Na0.5NbO3, where the direction of the maximum d33maxo* is rotated by 90° with an increasing temperature, and its amplitude attains the largest value in the high-temperature range when approaching the tetragonal phase.

Figure 10.

Figure 10

The piezoelectric coefficient in the orthorhombic K0.5Na0.5NbO3 as a function of angle θ under various temperatures in planes of φ = 0.

Figure 11.

Figure 11

The piezoelectric coefficient in the orthorhombic K0.5Na0.5NbO3 as a function of angle θ under various temperatures in planes of φ = π/2.

Figure 12.

Figure 12

Maximum of piezoelectric coefficient and its corresponding angle θmax as a function of temperature for the orthorhombic K0.5Na0.5NbO3 in planes of φ = 0.

Figure 13.

Figure 13

Maximum of piezoelectric coefficient and its corresponding angle θmax as a function of temperature for the orthorhombic K0.5Na0.5NbO3 in planes of φ = π/2.

According to the calculated LGD-free energy-polarization relationship as plotted in Figure 1b, the flattening of the LGD-free energy well arising from temperature growth enhances dielectric susceptibility, as well as piezoelectric response. This tendency further endows stronger effects on the piezoelectric response of KNN single crystals in the tetragonal-orthorhombic transition instead of the orthorhombic-rhombohedral transition.

As for the low-temperature rhombohedral phase, the orientation dependence of d33r* can be given by

d33r*(θ,ψ)=d15rcosθsin2θd22rsin3θ+d31rsin2θcosθ+d33rcos3θ (9)

As displayed in Figure 14a–c, similar three-dimensional surfaces of d33r* were observed at temperatures of 50 K, 75 K and 100 K, implying that the temperature variation in the rhombohedral phase causes less impact on the three-dimensional surface of d33r* in comparison with those for the tetragonal and orthorhombic phase. Since no lower-symmetry phase exists as the temperature is approaching toward 0 K, the rhombohedral phase is the most stable one, and the three-dimensional surface of d33r* remains unchanged when the K0.5Na0.5NbO3 single crystal was gradually frozen during the cooling process.

Figure 14.

Figure 14

The orientation dependence of coefficient of K0.5Na0.5NbO3 single crystals in the rhombohedral phases at the temperature of (a) 50 K, (b) 75 K, (c) 100 K.

It is found that d15r, d22r (negative value) are proportional to the temperature, while d32r and d33r are almost temperature independent in the rhombohedral phase (Figure 3). As a result, the three-dimensional surface of d33r slightly varies with varying temperatures, as shown in Figure 14a–c. At 50 K, the maximum d33r* of 284.444 pC/N lies along the direction defined by θ = 60.9° and φ = 0 (Figure 14a), while at 100 K, the maximum d33r* switches to the direction defined by θ = 61.1° and φ = 0 with an amplitude of 327.5 pC/N (Figure 14c). The dependence of the piezoelectric coefficient d33r* in KNN on the θ under various temperatures is revealed in Figure 15. The direction of the maximum value of d33r* varies with rising temperatures from 0 K to 130 K in the rhombohedral phase (Figure 16). Both maximum d33maxr* and its corresponding angle θmax are proportional to the temperature. The angles θ are higher than θ = 54.73°, which is consistent with the [001]c (or [111]r) direction.

Figure 15.

Figure 15

The piezoelectric coefficient in the rhombohedral K0.5Na0.5NbO3 as a function of angle θ at various temperatures.

Figure 16.

Figure 16

Maximum and its corresponding angle θmax as a function of temperature for the rhombohedral K0.5Na0.5NbO3.

According to the expression of d33r* in Equation (9), d33r* reveals an asymmetry attribute with respect to the axis defined by θ = 90°. It is obvious that the enhanced dielectric susceptibility, which is perpendicular to the polar direction, renders the large change in d15r. The polarization rotation near the phase transition region gives rise to the increase of piezoelectric response upon the heating process, which brings about the rotation of the maximum d33maxr* and the slight variation in d33r. Furthermore, with respect to the LGD-free energy profile (Figure 1c), the delayering of the free energy well with increasing temperatures indicates that the piezoelectric coefficients enhance toward a no-polar direction.

4. Conclusions

In summary, LGD thermodynamic theory was utilized to investigate the temperature-induced phase transition and evolution of three-dimensional d33* surface in KNN single crystals. The dielectric softening along the direction perpendicular to the polarization axis is responsible for the direction change of the maximum d33* under various temperatures. During the ferroelectric phase transition, the increase of shear piezoelectric coefficients renders a significant enhancement in d33* along the non-polar direction. This work not only looks into the fundamental understanding of the temperature-dependent phase transitions, but also paves the way for the optimization of piezoelectric properties in ferroelectric materials.

Acknowledgments

The authors would like to thank the National Natural Science Foundation of China (Grant No. 62074027).

Author Contributions

Conceptualization, Y.S. and G.X.; methodology, Y.S.; software, Y.S.; validation, Y.S. and G.X.; formal analysis, W.L. and C.C.; investigation, W.L.; resources, W.L.; data curation, W.L. and Y.S.; writing—original draft preparation, W.L. and Y.S.; writing—review and editing, Y.S.; visualization, W.L. and C.C.; supervision, Y.S. and G.X.; project administration, Y.S.; funding acquisition, Y.S. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China (Grant No. 62074027).

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

Footnotes

Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.


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