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Ferroelectricity of Orthorhombic and Tetragonal MAPbBr Single Crystal Zhang-Ran Gao, Xiao-Fan Sun, Yu-Ying Wu, Yi-Zhang Wu, Hong-Ling Cai, and XiaoShan Wu J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.9b00776 • Publication Date (Web): 01 May 2019 Downloaded from http://pubs.acs.org on May 1, 2019

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The Journal of Physical Chemistry Letters

Ferroelectricity of Orthorhombic and Tetragonal MAPbBr3 Single Crystal Zhang-Ran Gao, Xiao-Fan Sun, Yu-Ying Wu, Yi-Zhang Wu, Hong-Ling Cai,* and X. S. Wu* Collaborative Innovation Center of Advanced Microstructures, Laboratory of Solid State Microstructures & School of Physics, Nanjing University, Nanjing 210093, People’s Republic of China AUTHOR INFORMATION Corresponding Author *(H.-L.C.) E-mail: [email protected] *(X.S.W) E-mail: [email protected]

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ABSTRACT Hybrid organic-inorganic halide perovskites (HOIPs) MAPbBr3 and their ramifications have emerged for their photovoltaic, optical and other fascinating performances in recent years. However, many intrinsic properties, such as crystal structure and ferroelectricity, are still controversial. In this work, the ferroelectricity of orthorhombic and tetragonal MAPbBr3 single crystal was confirmed through the dielectric behavior vs. bias electric field ε(E), the temperature-dependent pyroelectric current with positive/negative poling and the positive-up-negative-down (PUND) measurements. The electric field dependence of dielectric constant curves show a butterfly type shape at orthorhombic and tetragonal phase. The pyroelectric current show two maximum values at 155 K and 245 K, corresponding ferroelectric-ferroelectric and ferroelectric-paraelectric phase transitions. Particularly, the direction of pyroelectric current can be reversed by positive or negative poling electric field, which is the assertive evidence of ferroelectricity. The PUND measurements act as the most convincing proof of the ferroelectricity of MAPbBr3 single crystal. This work reports new evidences of the ferroelectric properties of MAPbBr3 single crystal, which provides the intrinsic property when considering their large power conversion efficiencies.

KEYWORDS Polarization PUND DSC Pyroelectric Dielectric.


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Perovskite materials have been extensively researched in the past several decades due to their remarkable properties, such as, giant magnetoresistance (GMR), ferroelectricity, and superconductivity.1-6 Hybrid organic-inorganic halide perovskites (HOIPs), such as MAPbX3 (MA=CH3NH3+, X=I-, Br-, Cl-) and their ramifications have emerged for their photovoltaic, optical and other fascinating performances in recent years.7-17 Devices based on these materials such as sensors, solar cells and LEDs have been performed. For instance, the power conversion efficiencies (PCE) of the HIOPs MAPbI3 solar cells has been promoted from 3.8% to more than 22.1% since 2009, approaching the PCE of single crystalline silicon solar cell.18 However, MAPbI3 is unstable in atmosphere and will decompose at room condition in 48 hours. Meanwhile MAPbBr3 is a promising alternative to MAPbI3 with higher stability toward air and moisture. The ultrasensitive detectors based on MAPbBr3 were reported since the Photoluminescence (PL) spectrum of MAPbBr3 crystal can be modulated by different environments.19-21 Although the excellent performance and low manufacturing cost of MAPbX3 are well known, its intrinsic properties such as crystal structure and ferroelectricity remain controversial. MAPbI3 and MAPbBr3 share similar reversible structural phase transition. MAPbI3, who belongs to a tetragonal structure at room temperature, experiences a structural transition to a cubic phase above 330 K, and an orthorhombic phase below 165 K. MAPbBr3 experiences more structural phase transitions compared to MAPbI3.20 MAPbBr3 is a cubic phase (phase I) at room temperature. It undergoes transitions to a tetragonal phase (phase II) at 235 K, another tetragonal phase (phase III) at 155 K, and an orthorhombic phase (phase IV) at 150 K. Although MAPbI3 belongs to a tetragonal symmetry at room temperature, its space group and ferroelectricity are still under massive debate in the past several years. Many researchers suggested that MAPbI3 has


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a non-polar space group of I4/mcm, thus discredits the possibility of ferroelectricity at room temperature.22-24 Meanwhile, other studies have shown that MAPbI3 is in the I4cm polar space group at room temperature and has ferroelectricity. Its domain walls have also been reported.25-31 However, some other researchers reported that MAPbBr3 belongs to a non-polar cubic space —

group of Pm3m at room temperature.32-34 The space group and spontaneous polarization behavior of tetragonal or orthorhombic MAPbBr3 single crystal at low temperature are still lack of investigation.35-38 The space group of orthorhombic phase IV was reported to be polar Pna21 by A. Poglitsch and D. Weber in 1987,37 and was confirmed by K. Gesi in 1997.35 The recent investigations through Synchrotron X-ray Powder Diffraction suggests that the space group of orthorhombic phase is non-polar space group of Pnma.33,

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The tetragonal phase II was

determined to be I4/mcm at first by A. Poglitsch and D. Weber.37 However, it has to be noted that the polar space group I4cm and non-polar I4/mcm have exactly the same octahedron-tilt system, and the only difference is that I4cm is also polar along the c-direction. The interpretation of data from diffraction-based techniques depends on the user’s choice of the model to which the diffraction pattern should fit. Small deviations between I4/mcm and I4cm can rarely be clearly distinguished. That is the reason of that the recent article refuse to determine the exact space group of tetragonal phase II.20 Despite massive diligent researches have been performed, opinions regarding the aforementioned fundamental properties are contradicting in the past decades, and further work is demanded to reconcile these conflicts. Generally, ferroelectric properties only exist below the Curie temperature (TC), in which the crystal lattice must adopt one of 10 polar point groups: 1(C1), m(C1h), 2(C2), mm2(C2v), 3(C3), 3m(C3v), 4(C4), 4mm(C4v), 6(C6), 6mm(C6v). When temperature exceeds Tc, ferroelectrics will meet reversible structural phase transition from ferroelectric phase to paraelectric phase,


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accompanied by heat flow, dielectric and pyroelectric anomaly, ferroelectric domain wall motion and ferroelectric hysteresis loops. To determine the presence/absence of ferroelectricity, many functionally relevant properties should be performed simultaneously, such as piezoelectricity, pyroelectricity and P-E hysteresis. Here, high quality single crystals of MAPbBr3 were grown from the solution. We systematically investigate the intrinsic properties of high-quality MAPbBr3 single crystals by means of differential scanning calorimetry (DSC), dielectric anomalies, temperature-dependent pyroelectricity, bias electric field dependent dielectric constant, and positive-up-negative-down (PUND) measurements, which discloses the ferroelectricity of MAPbBr3 single crystal. High quality of bulk single crystals with minimum structural defects empowered us to investigate the intrinsic properties of these materials. It is the best way to explore the dielectric and ferroelectric properties of HOIPs that would be to exploit the single crystals. The MAPbBr3 single crystal was prepared by Antisolvent method. 10.0 mmol PbBr2 (AR, 99.0%, Aladdin) and 10.0 mmol MABr (99.99%, p-OLED) were dissolved in dimethylformamide (DMF) at room temperature in a small crystallizing basin forming saturated solution. To confine antisolvent vapor diffusion, cover the basin with a perforated tinfoil. The covered crystallization basin was then placed inside a deeper, larger, crystallizing basin, which contained methylbenzene (antisolvent). Sealing the outer crystallizing basin with tinfoil to create a balanced antisolvent atmosphere. MAPbBr3 crystals were grown from equimolar solution by slow vapor of methylbenzene into the dimethylformamide. DSC was measured in the temperature range of 120−273 K with a heating or cooling rate of 10 K/min under a nitrogen atmosphere on a NETZSCH DSC 200F3. The single crystals were cut into thin plate along direction for dielectric, pyroelectric, PUND measurement. Silver


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conductive paste deposited on the plate surfaces was used as the electrodes. Temperaturedependent complex dielectric permittivity at the frequency of 5 Hz to 1 MHz and bias electric field dependent dielectric permittivity were measured with a Tonghui TH2828A LCR meter. The pyroelectric current were measured with a constant heating rate on an electrometer (Keithley 6517B). The PUND current is measurement by homemade instrument which contains waveform generator (Agilent 33500B), high voltage waveform amplifier (Trek Model 609E-6), and electrometer (Keithley 6517B). The thickness of the MAPbBr3 single crystal is about 1 mm.

Figure 1. (a) XRD pattern of single crystal shows (010), (020), (030), (040) and (050) diffraction peaks. The inset shows topography of the single crystal. (b) XRD pattern with Rietveld refinement for polycrystalline MAPbBr3. The observed XRD intensity were marked by the black crosses, the Rietveld refinement result was presented red solid line, the Bragg reflections were marked by pink vertical lines, and the difference between observed and calculated intensity were denote green dots.


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XRD of powder sample and single crystal were performed at room temperature (Fig. 1) in order to determine the structure and purity of compounds. The XRD pattern of the powder —

sample (Fig. 1b) can be indexed according to the MAPbBr3 structure with a space group of Pm3 m, which proves the purity of the samples. The XRD patterns for the cubic samples at room temperature can be well refined using the standard Rietveld program GSAS with an Rwp factor within 13%. MAPbBr3 single crystals are pretty stable without any decomposition or deliquescence at room condition for several months. The XRD pattern of single crystal only has (010), (020), (030), (040) and (050) diffraction peaks, which proves very good crystallinity and the measured plane is along b-axis.

DSC(W/g)

c bi Cu

0.5

al on ag tr Te

1.0 (a)

c bi hm or th or

Heating

0.0

Cooling

-0.5 c bi Cu

180

al on ag tr Te

-1.0

c bi hm or th or

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


5KHz 10KHz 100KHz 1MHz

(b)

150

Dielectric constant(ε')

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120 90

Heating 5KHz 10KHz 100KHz 1MHz

(c) 100

80

60

Cooling

120

140

160

180

200

220

Temperature(K)

240

260

Figure 2. (a) The temperature dependence of Differential Scanning Calorimeter of MAPbBr3 single crystal along direction in the heating and cooling runs. (b) The temperature dependence of the real part of the dielectric constant of MAPbBr3 in heating runs. (c) The temperature dependence of the real part of the dielectric constant of MAPbBr3 in cooling runs.


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Differential Scanning Calorimeter measurements act a very important role in interpreting phase transition behaviors. Compared with stable reference materials, ferroelectric crystals will absorb or release latent heat during ferroelectric-to-paraelectric and/or ferroelectric-toferroelectric phase transitions. The temperature-dependent DSC curve (Fig. 2a) shows three endothermic peaks at T3 = 144 K, T2=151K and T1 = 239 K in the heating run and three exothermic peaks at around T!! = 233 K T!! = 158K and T!! =154K in the cooling run. These results reveals three couples of reversible phase transitions. The value of enthalpy change ΔH can be integral from the peak area of DSC anomalies, and the entropy changes of phase transitions can be calculated as ΔS = ΔH/T. The entropy change (ΔS) at around T1, T2 and T3 estimated from the DSC are about 1.13J/mol·K and 28.47 J/mol·K. Three apparent thermal hysteresis indicate first-order phase transitions.


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Figure 3. Real part of dielectric response of MAPbBr3 crystal along its direction measured at 100 KHz as a function of applied bias electric field at temperature of (a) 170 K and (b) 120 K. The red arrows in (a) indicate the polarization direction of ferroelectric domains.

Appearance of large dielectric anomalies in the vicinity of phase transition is an essential characteristic of spontaneous polarization. The temperature-dependent permittivity ε

(real part

of complex dielectric constant) along direction in heating and cooling process with the temperature range of 120-273 K are depicted in Fig. 2b and 2c, respectively. The permittivitytemperature curves display reversible sharp peak at T3 = 144 K and T!! =162 K in heating and cooling process corresponding the phase transition between tetragonal and orthorhombic. Some small dielectric anomalies occur at the temperature of T1 = 240 K and T!! = 243 K and in heating and cooling process, corresponding the phase transition between cubic and tetragonal phase. The dielectric anomalies with various frequencies are consistent with the DSC curves. The insulating ferroelectrics whose leakage currents are negligible usually show a typical polarization–electric field (P-E) hysteresis loops, which is the direct evidence of ferroelectricity. However, the leakage current will impede the interpretation of P-E loop measurement in some finite resistance ferroelectrics. Fortunately, the relative permittivity dependence of bias electric field curve 𝜀(E) can also indicate the absence or presence of ferroelectricity.40, 41 The correct description of the 𝜀(E) curve is connection with other characteristics of the nonlinear response, like ferroelectric polarization hysteresis loop. Several theoretical models have been proposed to fit the interesting dielectric behavior in ferroelectrics.41-43 The most creditable theory is a phenomenological one presented by Eiras et al.,41 which provided a helpful path to verdict the


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existence of ferroelectricity when the P-E hysteresis loop is affected by the conduction mechanism. It suggests that the hysteresis 𝜀(E) curve is a necessary and sufficient condition to the P-E hysteresis loop. The value of the bias electric field, which corresponds maximum permittivity in 𝜀 (E) curve, represents the coercive field. Rakita et al. claimed that the polarization value can be simply obtained by integrating ε over the bias electric field, based on the following equation31: 𝛥𝑃 = 𝜀! ∫ 𝜀 · 𝜕𝐸 Therefore, the 𝜀(E) hysteresis is another direct evidence of ferroelectricity. The real part ε’ of MAPbBr3 still dominates its complex permittivity ε, like PZT40 and Rochelle salt (Potassium Sodium Tartrate, KNa(OC(O)C(OH))2 4H2O). The real part permittivity ε’ as a function of electric field of tetragonal and orthorhombic MAPbBr3 single crystal along direction are shown in Fig. 3a and 3b, respectively. The dielectric constant has a small value as poling with a positive electric field since all the domains are polarized up. The domains with polarization up decreases, while those with polarization down increases when the electric field decreases. The dielectric constant increases and reaches a maximum value at a negative electric field where the domains with polarization up are equal to those with polarization down. The value of the bias electric field, which corresponds maximum permittivity in ε(E) curve, represents the coercive field. The dielectric constant decreases with further decreasing of electric field. All the domains are polarized down when the electric field reaches a negative saturated value. Another maximum value of dielectric constant will appear when the electric field reaches the positive coercive field. Therefore, the presence hysteresis loop of ε(E) curve is a direct evidence of the ferroelectricity.


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The MAPbBr3 crystals are affirmative ferroelectric below the Curie temperature. The coercive field Ec of the MAPbBr3 is about 1.0 KV/cm for both tetragonal and orthorhombic phase.

Figure 4. The temperature-dependent pyroelectric currents (dots, right coordinate) of the single crystal poled by opposite electric voltages (±400 V) and the temperature dependence of polarization (lines, left coordinate) given by integration of pyroelectric currents.

Since ferroelectrics definitely belongs to pyroelectric materials, the spontaneous polarization of ferroelectrics can be obtained from pyroelectric current. When temperature-dependent spontaneous polarization changes, the excess free charges appear on the polar surfaces of ferroelectrics. This phenomenon give rise to the detectable pyroelectric current in the circuit between the two opposite polar surface. Herein the single crystal of MAPbBr3 was cut into thin plate, which was first poled by an electric field of 400 V (or -400 V) during the cooling process. The pyroelectric currents of MAPbBr3 were measured under zero electric field in the heating


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processes along direction. The temperature-dependent pyroelectric currents were recorded (Fig. 4), where peaks with value of 0.013 nA (-0.012 nA) and 0.059 nA (-0.056 nA) were observed at 155 K and 245 K, respectively, after poling with a 400 V (-400 V) electric field, indicating the release of screen charges. The inverse of current direction after the inverse of the poling electric field indicates that the polarization can be switched by external electric field, which reveals that the crystal has ferroelectricity in tetragonal and orthorhombic phase. By integrating the pyroelectric current i in the circuit between two polar surfaces in a heating process, the temperature dependence of spontaneous polarization (Ps) can be obtained:

Ps=∫

! !"

𝑑𝑇,

Where R is the heating or cooling rate and A is the area of the sample. The spontaneous polarization can reach about 0.35 μC/cm2 in tetragonal phase and about 0.4 μC/cm2 in orthorhombic phase. As the appearance of ferroelectricity in orthorhombic and tetragonal MAPbBr3, the space group of orthorhombic and tetragonal MAPbBr3 are Pna21 and I4cm respectively.


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Figure 5. Hysteresis loops of electric polarization measured with a positive-up-negativedown (PUND) measurements at 170 K (a) and 120 K (b).

To confirm the ferroelectricity, the measurements of precise positive-up-negative-down (PUND) measurements were taken (Figures S3 and S4), and the polarization−electric field (P−E) hysteresis loops are calculated from the current (Fig. 5). As a finite resistance crystal, the leakage current will impede the interpretation of P-E loop measurement in traditional P−E hysteresis loops measurement. PUND measurement can get rid of the disturbance of leakage current and provide the true ferroelectric response. Fig. 5 shows the P-E hysteresis loop of MAPbBr3 single crystal given by PUND measurements along direction in the tetragonal and orthorhombic phase. It confirms the coercive fields (Ec) of MAPbBr3 single crystal is about 1.0 KV/cm in both tetragonal and orthorhombic phase. Meanwhile, the spontaneous polarization given by PUND measurements are about 0.4 μC/cm2 and 0.6 μC/cm2 for the tetragonal and orthorhombic phase,


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which are consistent with the pyroelectric measurement. This is the most direct and powerful evidence for the ferroelectricity of MAPbBr3 single crystal. In conclusion, the ferroelectricity of semiconductor MAPbBr3 is investigated in this work. It is a large challenging to prove its ferroelectricity since the leaky current of semiconductor ferroelectric materials. The presence of traditional P-E hysteresis loop is impeded here as abovementioned reasons. The butterfly-like electric field-dielectric ε(E) hysteresis curve, the switchable pyroelectric current direction by poling voltage and the PUND measurements act as the direct evidence for the ferroelectric of orthorhombic and tetragonal MAPbBr3 along . The determination of ferroelectricity of orthorhombic and tetragonal MAPbBr3 provides a necessary property for considering power conversion efficiency of hybrid organic-inorganic halide perovskites.

FIGURES


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Figure 1. (a) XRD pattern of single crystal shows (010), (020), (030), (040) and (050) diffraction peaks. The inset shows topography of the single crystal. (b) XRD pattern with Rietveld refinement for polycrystalline MAPbBr3. The observed XRD intensity were marked by the black crosses, the Rietveld refinement result was presented red solid line, the Bragg reflections were marked by pink vertical lines, and the difference between observed and calculated intensity were denote green dots.

DSC(W/g)

c bi Cu

0.5

al on ag tr Te

1.0 (a)

c bi hm or th or

Heating

0.0

Cooling

-0.5 c bi Cu

180

al on ag tr Te

-1.0

c bi hm or th or

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


5KHz 10KHz 100KHz 1MHz

(b)

150

Dielectric constant(ε')

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120 90

Heating 5KHz 10KHz 100KHz 1MHz

(c) 100

80

60

Cooling

120

140

160

180

200

220

Temperature(K)

240

260

Figure 2. (a) The temperature dependence of Differential Scanning Calorimeter of MAPbBr3 single crystal along direction in the heating and cooling runs. (b) The temperature dependence of the real part of the dielectric constant of MAPbBr3 in heating runs. (c) The temperature dependence of the real part of the dielectric constant of MAPbBr3 in cooling runs.


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Figure 3. Real part of dielectric response of MAPbBr3 crystal along its direction measured at 100 KHz as a function of applied bias electric field at temperature of (a) 170 K and (b) 120 K. The red arrows in (a) indicate the polarization direction of ferroelectric domains.

Figure 4. The temperature-dependent pyroelectric currents (dots, right coordinate) of the single crystal poled by opposite electric voltages (±400 V) and the temperature dependence of polarization (lines, left coordinate) given by integration of pyroelectric currents.


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Figure 5. Hysteresis loops of electric polarization measured with a positive-up-negativedown (PUND) measurements at 170 K (a) and 120 K (b).

ASSOCIATED CONTENT Supporting Information. Figure S1, the schematic diagram of single crystal growth for MAPbBr3. Figure S2, the crystal face of MAPbBr3 single crystal. The leakage current will impede the interpretation of P-E loop measurement in some finite resistance ferroelectrics like MAPbBr3. Figures S3 and S4, the time-current relationship in positive-up-negative-down (PUND) measurements. AUTHOR INFORMATION Corresponding Authors *(H.-L.C.) E-mail: [email protected] *(X.S.W) E-mail: [email protected]


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Notes The authors declare no competing financial interests. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundations of China (11574138, 11874200, 21427801), the Top-Notch Young Talents Program of China, the National Key R&D Program of China (2016YFA0201104), and Dengfeng Project B of Nanjing University. REFERENCES

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Figure 1. (a) XRD pattern of single crystal shows (010), (020), (030), (040) and (050) diffraction peaks. The inset shows topography of the single crystal. (b) XRD pattern with Rietveld refinement for polycrystalline MAPbBr3. The observed XRD intensity were marked by the black crosses, the Rietveld refinement result was presented red solid line, the Bragg reflections were marked by pink vertical lines, and the difference between observed and calculated intensity were denote green dots. 84x65mm (300 x 300 DPI)


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Figure 2. (a) The temperature dependence of Differential Scanning Calorimeter of MAPbBr3 single crystal along direction in the heating and cooling runs. (b) The temperature dependence of the real part of the dielectric constant of MAPbBr3 in heating runs. (c)The temperature dependence of the real part of the dielectric constant of MAPbBr3 in cooling runs. 84x96mm (300 x 300 DPI)



Figure 3. Real part of dielectric response of MAPbBr3 crystal along its direction measured at 100 KHz as a function of applied bias electric field at temperature of (a) 170 K and (b) 120 K. The red arrows in (a) indicate the polarization direction of ferroelectric domains. 84x93mm (300 x 300 DPI)


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Figure 4.The temperature-dependent pyroelectric currents (dots, right coordinate) of the single crystal poled by opposite electric voltages (±400 V) and the temperature dependence of polariza-tion (lines, left coordinate) determined by integration of pyroe-lectric currents. 272x200mm (300 x 300 DPI)



Figure 5. Hysteresis loops of electric polarization measured with a positive-up-negative-down (PUND) measurements at 170 K (a) and 120 K (b). 50x74mm (300 x 300 DPI)


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Ferroelectricity of the Orthorhombic and Tetragonal ... - ACS Publications

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