Optimized Growth of Large-Sized LiInSe2 Crystals and the Electric

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Optimized Growth of Large-sized LiInSe2 Crystals and the Electric-Elastic Properties Ning Jia, Shanpeng Wang, Zeliang Gao, Qian Wu, Chunlong Li, Xixia Zhang, Tongtong Yu, Qingming Lu, and Xu-Tang Tao Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00964 • Publication Date (Web): 02 Oct 2017 Downloaded from http://pubs.acs.org on October 6, 2017

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Crystal Growth & Design

Optimized Growth of Large-sized LiInSe2 Crystals and the Electric-Elastic Properties †

Ning Jia, Shanpeng Wang,*,

†,

‡

Zeliang Gao,

*, †, ‡

Qian Wu,

†

Chunlong Li,

†

Xixia Zhang,

†

TongTong Yu, † Qingming Lu, § and Xutang Tao*, †, ‡

† State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, China ‡ Key Laboratory of Functional Crystal Materials and Device (Shandong University, Ministry of Education), Jinan 250100, China § School of Chemistry and Engineering, Shandong University, Jinan, 250100, China

ABSTRACT: Single crystals of environmental friendly material LiInSe2 (LISe) with dimensions up to Ф16 mm × 55 mm were grown successfully through a modified vertical Bridgman technique. The quality of the crystal was measured by high resolution X-ray diffraction rocking curve, and a full width at half-maximum (FWHM) for a, b, and c faces are 47″, 46″, 36″, respectively. It indicates that the as-grown crystal is high quality. The complete sets of dielectric, elastic, and piezoelectric constants of LISe crystals at room temperature were obtained by the resonant technique and impedance analysis for the first time. The piezoelectric constants d24 and d33 reached -13.6 pC/N and 8.5 pC/N, respectively. The corresponding electromechanical coupling coefficients k33 is 21%. In addition, the structural distortions and dipole moments of

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LISe were analyzed in detail. Our results show that LISe is a promising candidate as environmental friendly piezoelectric material.

INTRODUCTION

Piezoelectric crystals are dominantly used in sensors, actuators, transducers, transformers, etc., for various electromechanical devices.1-3 Lead-based piezoelectric materials with excellent piezoelectric and electromechanical coupling properties, such as PbZrO3-PbTiO3 (PZT) and Pb (Nb, Mg)-PbTiO3 (PMN-PT) solid solution systems, are the widely used piezoelectric materials.4-7 Due to the environmental and health hazards of Pb, the extensively searching for lead-free piezoelectric materials has become a challenge and particular interest. LiInSe2 (LISe) is a promising candidate as environmentally friendly lead-free piezoelectric material. LISe crystallizes with the β-NaFeO2 structure (orthorhombic mm2 symmetry group). It is a wellknown mid-infrared nonlinear optical crystal to realize 3.6-4.8 and 7-12 µm widely tunable laser output8-13 and a promising candidate for semiconductor radiation detection application.14-17 LISe belongs to a noncentrosymmetric (NCS) structure with a large structural distortion which gives rise to large piezoelectric effect. It has a high melting temperature of 920 oC and no phase transitions below the melting point. Therefore, it could possibly be used in high temperature piezoelectric areas. However, up to date, there have been no complete research on the dielectric, elastic, and piezoelectric properties of LISe single crystals.


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In this work, large-sized and high quality LISe single crystals were successfully grown by modified Bridgman method. The complete sets of dielectric, elastic, and piezoelectric constants of LISe crystal were determined for the first time. Moreover, the relationship between crystal structure and piezoelectric properties is also discussed. The results indicate that LISe is a promising candidate as environmental friendly piezoelectric material.

EXPERIMENTAL SECTION

Polycrystalline synthesis and crystal growth of LISe. The crystalline synthesis and bulk crystal growth of LISe were reported in our preliminary research.18 However, cracks would occurred in the crystals and the crystal size was also limited. This work is focused on optimizing the polycrystalline synthesis and growth parameters for LISe single crystal. After a great deal of attempts, larger-sized single crystals with higher quality were obtained. Single-phase polycrystalline LISe were synthesized using the traditional solid-state reaction techniques. High purity Li ( 99.9% ), In ( 99.999% ), and Se ( 99.999% ) in stoichiometric ratio of Li : In : Se = 1 : 1: 2, with 0.1% excess of Li and 0.2% Se, were placed in a graphite crucible. The crucible was then sealed in quartz ampoule evacuated to 1.0 × 10-3 Pa. Afterwards, the quartz ampoule with raw materials was placed in the center of a vertical, programmable temperature furnace. A stepwise heating program of the furnace was designed as follows: heated from room temperature to 300-350 °C at a speed of 30 °C h-1 and kept at this temperature for 24 h to avoid explosion of the quartz ampoule, then heated to 680-730 °C at a speed of 20 °C h-1 and held at this


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temperature for 24 h to ensure the complete reaction between Se and Li, afterwards raised to 910-940 °C. The temperature was oscillated between 910 and 940 °C for two times, and the period of oscillation was 2 h, which was used to make the raw materials mixing uniformly and reacting completely. After forming a homogeneous melt, the furnace was cooled at 50 °C h-1 to room temperature. The furnace temperature was controlled by an FP23 temperature controller (SHIMANDEN). Crucible explosion can be avoided using this method. In each run, 180-200 g single-phase LISe polycrystalline could be obtained with high efficiency.

Figure 1. Photograph of polycrystalline LISe ingot (a) synthesized previously and (b) in this work.


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Figure 2. (a) Axial temperature field of modified Bridgman furnace; (b) Schematic diagram of vertical Bridgman furnace for LISe growth.

LISe single crystal growth was performed by a modified vertical Bridgman method through spontaneous nucleation in a three-zone vertical furnace. Fig. 2 shows the schematic diagram of the vertical Bridgman furnace and the temperature distribution. The synthesized material was loaded into a graphite crucible with a coniform tip. Then the crucible sealed in a quartz ampoule evacuated to 1×10−3 Pa at room temperature. The temperature in the upper zone was about 950960 °C, and the lower zone was about 840-850 °C. During the growth of the LISe, the temperature gradient at the melting point (910 ± 5 °C) was set to be 10-15 °C/ cm.

It was worth noting that a dynamic adjustment of rotating speed and a smaller cooling rate were adopted in order to stabilize the metastable growth and improve the crystal quality. Before crystal growth commenced, the crucible was placed in the upper zone of the furnace for 24 h. After the polycrystalline LISe was completely melted, the accelerated crucible rotation technique (ACRT) was used to make the melt homogenous. At the beginning of the growth, the crucible


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rotated at 15-20 r min-1 at the center of the furnace, and the rotation speed was slowly changed to 10-15 r min-1. Then the crucible was pulled down with a velocity of 1-1.5 mm h-1 from the upper zone to the gradient zone and ended in the lower zone. When the crystal growth was completed, the furnace was then held at 840-850 °C for 48 h to anneal the crystal. Finally, the single crystal was cooled to room temperature at a rate no more than 20 °C h-1 to avoid cracks. After the growth optimization, a high-quality and crack-free LISe single crystal was obtained.

Figure 3. Photograph of LISe single crystals (a) before and (b) after growth optimization grown by vertical Bridgman method.

Electrical characterization. As a multifunctional NCS material, LISe belongs to the orthorhombic system. Its space group is Pna21 with a = 7.1976 Å, b = 8.4159 Å and c =6.7986 Å. LISe has 17 independent nonzero electro-elastic constants: 3 independent dielectric constants (εij), 9 independent nonzero elastic constants (sij) and 5 independent nonzero piezoelectric


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constants (dij). Before the electrical, electromechanical, and elastic properties evaluation, the relationships between the piezoelectric axes and crystallographic axes should be established. According to the Institute of Electrical and Electronics (IEEE) standard19, the X, Y and Z axes are along the crystallographic a, b and z axes, respectively, in this piezoelectric coordination. A schematic of the 10 samples with different orientations is shown in Figure 4. These samples are divided into two kinds: non-circumgyrate samples and circumgyrate samples, as shown in Table 1. For non-circumgyrate samples, the first letter denotes the thickness direction, the second one denotes the length direction. For circumgyrate samples, the former two letters denote the same meaning as in the non-circumgyrate samples, while the third and fourth letters mean the rotation direction and rotation angle. The dimensions of the rectangular bars were typically 8 × 3.5 × 2 mm3, and 6 × 6 × 2 mm3 for square bars and 4 × 4 × 10 mm3 for the z bar. The dimensional variations in each sample were less than 3%. All the samples were sputter coated with silver on parallel surfaces along the direction of the applied alternating current electric field. The sample detailed shapes and orientations, and the corresponding elastic and piezoelectric constants are listed in Table 1. Then the dielectric, electromechanical, and elastic properties were investigated by means of the resonance technique using an Agilent 5294A impendence network analyzer.

Dielectric Properties. The dielectric constant of the crystal is an important macroscopic quantity that can reflect the polarization behavior of the dielectric. The LISe, an orthorhombic crystal, has three independent dielectric constants, ε11, ε22 and ε33, which can be obtained from


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the capacitances of the X, Y and Z square pieces, respectively. All the dielectric constants can be obtained from the capacitance measurement at 1 kHz according to the following formula:

= | = 1,2,3

(1)

Where C is the capacitance, t is the thickness, A is the area of the measured plate, and ε0 is the vacuum dielectric constant.

Elastic and Piezoelectric Properties. As a polar crystal, the positive direction of the Z-axis and d33 was determined by a quasi-static piezoelectric d33 meter (model ZJ-2, Institute of Acoustic Academia Sinica, Beijing, China). It is noteworthy that piezoelectric constant d33 and elastic constant s33 were obtained by the resonance technique using equation (2) – (4). Piezoelectric constants d31, d32 and elastic compliance constants s11 and s22 were calculated using equation (2) – (4). Elastic compliance constants s44, s55, s66 were calculated using equation (5) – (8) and (11), where the electric field was applied along the length direction of the samples. Circumgyrate samples were used to determine the other piezoelectric and elastic constants, including d15, d24, s12, s13 and s23. With the former values of constants d31, d32, and d33, piezoelectric constants d24 and d15 were obtained according to equation (9) - (12) in a new coordinate system. Similarly, with the help of the circumgyrate samples, the elastic constants s12, s13 and s23 can be also determined. After obtaining all piezoelectric coefficients and elastic compliance constants, the stiffness coefficients cij can be obtained using equation (13). In


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conclusion, we get a complete set of dielectric, elastic and piezoelectric coefficients for LISe crystal for the first time.

=

(2)

=

!

tan

!

(3)

%& = & ' &&

(4)

( )*+45° = + + 2 + 00

( )*145° = + 22 + 22 + 33

( 22 4)+45° = + 22 + 22 +

( )*545° = + 00

( %2 )*145° =

√ %22

( 4)+45° %2 =

+ %2 − %

=

=

!

(7)

(9)

(10)

(11)

!

(6)

(8)

+ %2 − %3

√ %22

(5)

891 !

(12)

c =

(13)


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Figure 4. Schematic diagram of the samples for measuring the dielectric, elastic, and piezoelectric constants. Table 1. Summary of the crystal cuts for Dielectric, Piezoelectric and Elastic properties. No.

Sample

Sample size (mm3)

Electric field direction

Constants

1

x square

6×6×2

x

s55, ε11

2

y square

6×6×2

y

s44, ε22

3

z square

6×6×2

z

ε33

4

z bar

4 × 4 × 10

z

d33, s33

5

zx

8 × 3.5 × 2

z

d31, s11

6

zy

8 × 3.5 × 2

z

d32, s23

7

zxl(45°)

8× 3.5 × 2

x

s66


10

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8

yzw(45°)

8 × 3.5 × 2

y

d24, s23

9

zxt(45°)

8 × 3.5 × 2

z

s12

10

zxw(45°)

8 × 3.5 × 2

z/y

d15, s13

RESULTS AND DISCUSSION

Polycrystalline synthesis. After many designs and attempts, single-phase polycrystalline LISe ingot with weight about 180-200 g was obtained using the single temperature zone furnace, as shown in Fig. 1(b). It can be seen from the Fig. 1(b) that most parts of the ingot are uniform and compact, compared with Fig. 1(a) previous synthesized polycrystalline. It is worth to note that a lower cooling rate and dynamic adjustment of temperature oscillation during the synthesized process can obviously improve the polycrystalline quality. And it was confirmed to be high purity and single phase LISe polycrystalline by XRD characterization, as shown in Fig.5. The calculated XRD patterns were obtained from the single crystal structure data and calculated using a computer program named Mercury 3.3.


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Figure 5. Simulated and experimental powder X-ray diffraction patterns for LISe.

Crystal Growth. When the growth parameters is not appropriate, there are some cracks always appeared within the crystal. Fig. 3(a) shows the photograph of a LISe single crystal grown before optimization, the size of the crystal is about 16 mm in diameter and 60 mm in length. From the picture, we can see obviously that, cracks extending deep inside the main body of the crystal and resulting in fracture. It is assumed this unsuccessful growth is that the thermal gradient of the solid-liquid interface is so large to accelerate the crystallization and result in many grain. And another reason maybe the cooling rate and the speed of crucible pulled down are inappropriate. To get crack-free and higher quality single crystals, a good deal of optimize the growth parameters were attempted.

The crystal quality is heavily depending on the polycrystalline, thermal field, cooling rate and the speed of crucible pulled down. A higher quality crystal means its thermal field must be proper with the rate of pulling down. As described in the experiment section, different from the


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prior experiment parameters, a more stabilized thermal field, dynamic adjustment of crystal rotation speed, and a different crucible material, were adopted in the growth of LISe crystals. Finally, the cracks in the LISe crystal are overcome completely. As shown in Fig. 3(b), crackfree and high quality LISe single crystal of 16 mm in diameter, and 55 mm in length was successfully obtained.

The crystalline quality of the as-grown LISe crystal was checked by HRXRD. The X-ray rocking curve is a widely useful way to investigate the perfection of crystals. It can give information about the quality of different domains or zones of the crystals. For the same face of a specific crystal, the smaller of the full width at half maximum (FWHM), the higher quality of crystal. The XRD rocking curves of a, b, and c faces are shown in Fig. 6. As the results shown, the intensity of the diffraction peak is high, and the shape of the peak is symmetrical. The FWHM of the rocking curves for a, b, and c faces are 47″, 46″, 36″, respectively, indicating the as-grown crystal is of high quality.

Figure 6. Rocking curve for a, b, and c-cut LISe crystal and the corresponding FWHMs.


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Elastic and Piezoelectric properties. The elastic and piezoelectric properties of LISe are summarized in Table 2. Each constant was obtained by averaging several resonance peak values from the impendence analyzer. LISe crystal exhibits a better piezoelectric performance compared with LiInS2 and α-SiO2. The dielectric constants of LISe crystal, ε11, ε22 and ε33, were 8.98, 10.73 and 9.81, respectively, and exhibited a small anisotropy. The piezoelectric constants ( d15 = -7.79 pC/N, d31= -8.35 pC/N, d32= -4.24 pC/N, d33= 8.50 pC/N ) are larger than those of α-SiO2 ( d11 = -2.31 pC/N, d14= -0.73 pC/N）and approximately equal to LiInS2 (d15 = -10.20 pC/N, d31= -4.60 pC/N, d32= -6.30 pC/N, d33= 9.60 pC/N)20. The correct signs of the piezoelectric constants are determined by the means of the resonance technique and confirmed by the quasistatic state IJ-2 d33 meter. The electromechanical coupling coefficient is about two times as that of α-SiO2 and comparable to LiInS2. Our results indicate that the LISe crystals exhibit excellent piezoelectric properties, which makes LISe a potential environmental friendly candidate for sensor application. We believe that better piezoelectric property is not only relevant to the better quality of our crystals, but also associated with the distortion of crystal structure.


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Figure 7. Ball and stick diagram of InSe4 tetrahedron and LiSe4 tetrahedron in LISe. Note that the arrows indicate the dipole moment of the tetrahedrons, and the bond length is shown beside the bonds.

It is well known that the origin of the physical properties of crystal is related to its structure, as the piezoelectric, electro-optical, and second-order nonlinear properties intensity depend on the non-centrosymmetric microstructure.21 For a polar crystal such as LISe, the larger of the spontaneous polarization, the better of the piezoelectric properties it may exhibit.22 The structure of LISe contains asymmetric LiSe4 and InSe4 tetrahedrons, which are believed to account for the excellent piezoelectric properties. Furthermore, dipole moments were adopted to quantify the distortion of the asymmetric tetrahedron. The bond distances for Li-Se range from 2.578 - 2.600 Å, with respect to the In-Se from 2.621 - 2.637 Å, as shown in Fig. 7. It has been determined that the magnitude of dipole moment of LiSe4 is 2.9156 Debye, whereas the InSe4 is 1.0375 Debye. We obtained the two values by using a bond-valence approach to calculate the magnitude of the dipole moments (for the detailed calculation process the reader is referred to the provided ESI, Table S1 and Table S2). The total dipole moment in the unit cell is the sum of the dipole moments of all the tetrahedrons. And the magnitude of the net dipole moment of the unit cell is calculated to be 9.71 × 10-2 esu·cm/Å3. The directions of the dipole moments of the tetrahedrons and the unit cells are shown in Fig. 8. The direction of the total dipole moment is along the - c axis, which is in good agreement with the experimental results. In addition, the spatial


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distribution of all the piezoelectric coefficients was also analyzed. As shown in Fig. 9, θ and ϕ represent the rotation angle around Y- and Z-axis, respectively. And the maximum (14.65 pC/N) of the piezoelectric coefficients appears on d15 when its rotation angle are θ = 58° and ϕ = 0, respectively.

Figure 8. Directions of dipole moments of each LiSe4 and InSe4 tetrahedrons in LISe. The yellow and blue arrows indicate the directions of dipole moments for LiSe4 and InSe4 tetrahedrons, respectively. The red arrow indicates the directions of the net dipole moments for unit cell.

Table 2. Dielectric, Elastic and Piezoelectric Coefficients of LISe Crystal Dielectric Constants εii ε11

ε22

ε33


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LISe

8.98

10.73

9.81

LIS

12.01

10.96

12.77

α-SiO2

39.97

39.97

41.03 Elastic Coefficients sij (pm2/N)

s11

s12

s13

s22

s23

s33

s44

s55

s66

LISe

30.90

6.97

2.12

26.70

10.66

20.42

30.48

30.06

23.56

LIS

21.53

6.22

2.20

25.30

4.30

17.00

48.00

52.00

27.50

α-SiO2

12.77

-1.79

-1.22

0

0

9.60

20.04

0

29.12

Stiffness Constants cij (1010N/m2)

LISe

c11

c12

c13

c22

c23

c33

c44

c55

c66

3.44

-0.96

0.14

5.00

-2.51

6.19

3.28

2.77

4.24

Piezoelectric Constants dij (pC/N) d15

d24

d31

d32

d33

d14

d11

LISe

-7.80

-13.60

-8.40

-4.20

8.50

0

0

LIS

-10.20

-13.30

-4.60

-6.30

9.60

0

0

α-SiO2

0

0

0

0

0

-0.73

-2.31

Electromechanical Coupling Coefficients kij k31 LISe

9.10%

k32

k33

k24

k15

8.30% 21.00% 26.30% 16.60%


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Figure 9. Spatial orientation dependence of the piezoelectric constants d15. (b) Variations of d15 as a function of rotation angle around Y-axis. θ and ϕ represent the rotation angle around Y- and Z-axis, respectively.

CONCLUSIONS

High quality large-sized LISe single crystal with 16 mm in diameter and 55 mm in length was successfully grown by the Bridgman method. Dynamic adjustment of rotating speed and a


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smaller cooling rate are confirmed more suitable to grow high quality LISe single crystals. The complete set of the piezoelectric, elastic and dielectric constants of the LISe crystals have been investigated by the resonance technique for the first time. In addition, the crystal structure and dipole moments of LISe were also analyzed to illustrate the excellent piezoelectric performance within a certain range. It is expected that LISe is not only a potential nonlinear optical crystal but also a good candidate as environmental friendly piezoelectric material at room temperature.

Author information

Corresponding Author

* E-mail: [email protected] (Shanpeng Wang); [email protected] (Zeliang Gao); [email protected] (Xutang Tao)

Note The authors declare no competing financial interest. Funding Sources National Natural Science Foundation of China (Nos. 51572155, 51321091, 11504389), Shandong Provincial Natural Science Foundation, China (ZR2014EMM015), Independent Innovation Foundation of Shandong University, IIFSDU. National key Research and Development Program of China (2016YFB1102201)


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For Table of Contents Use Only

Optimized Growth of Large-sized LiInSe2 Crystals and the Electric-Elastic Properties †

Ning Jia, Shanpeng Wang,*,

†,

‡

Zeliang Gao,

*, †, ‡

Qian Wu,

†

Chunlong Li,

†

Xixia Zhang,

†

TongTong Yu, † Qingming Lu, § and Xutang Tao*, †, ‡

High quality and large-sized environmental friendly LiInSe2 crystals were successfully grown by Bridgman technique. The complete sets of dielectric, elastic, and piezoelectric constants of LiInSe2 crystals were obtained at room temperature. Our results show that LiInSe2 is a promising candidate as environmental friendly piezoelectric material.


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Optimized Growth of Large-Sized LiInSe2 Crystals and the Electric

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