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Self-organized ferroelectric domains controlled by a constant bias from AFM tip He Ma, Guoliang Yuan, Tom Wu, Yaojin Wang, and Jun-Ming Liu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b13982 • Publication Date (Web): 05 Nov 2018 Downloaded from http://pubs.acs.org on November 8, 2018

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ACS Applied Materials & Interfaces

Self-organized ferroelectric domains controlled by a constant bias from AFM tip He Ma1, Guoliang Yuan1,*, Tom Wu2, Yaojin Wang1, and Jun-Ming Liu3,* 1School

of Materials Science and Engineering, Nanjing University of Science and Technology,

Nanjing 210094, P. R. China 2School

of Materials Science and Engineering, University of New South Wales (UNSW), Sydney,

NSW 2052, Australia 3National

Laboratory of Solid State Microstructures Nanjing University, Nanjing 210093, P. R.

China

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ABSTRACT. The ferroelectric polarization switching along an external electric field are most important for the applications of ferroelectric memories, piezoelectric sensors and actuators, however the depolarization commonly occurs randomly and cannot be controlled exactly until now. Here a tip bias introduces the polarization switching and a ~10-m-scale domain in a triglycine sulfate crystal, and then the polarization backswitching as a special depolarization introduces a series of ordered granular domains along a line being parallel to the c axis and through the tip which divides the original domain to two similar parts. Such backswitching is controlled by the surface charge change as a result of the interplay among polarization charges, mobile H+ ions at surface and the strong crystal anisotropy. The self-organized ferroelectric domains offer us a new freedom to design novel ferroelectric or piezoelectric devices in future. KEYWORDS.

ferroelectric

domain,

polarization,

crystal

anisotropy,

surface

charges,

piezoresponse force microscopy


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INTRODUCTION The development of modern civilization is inherently enabled by technologies to manipulate and control information. Ferroelectric materials are distinguished from other polar dielectrics by their ability of polarization switching under an external electric field. The polarization can switch along the external electric field and keep well after such field is removed.1-3 This property is the basis of various ferroelectric devices such as piezoelectric sensors, actuators and non-volatile ferroelectric memories.1,4-6 However, the depolarization under zero external electric field is commonly treated as a harmful factor for device design and application nowadays, since it occurs randomly and cannot be controlled exactly in most cases. Depolarization commonly occurs first at domain walls with the highest domain-wall energy, especially some walls with the smallest radius of curvature.7 Besides, depolarization also occurs near some charged defects which allow a new reverse domain to nucleate and to grow inside a large domain.8 Therefore, it has been a big challenge to manipulate and control information through exactly controlled depolarization and reverse domains until now.9 The scanning probe microscopy (SPM) and surface ion dynamics may give us new freedoms to control surface charges, polarization and depolarization. Recently, polarization switching and domain growth have been widely studied under an electric field produced by SPM.3,10-17 These studies provide the information of polarization switching, depolarization, domain nucleation, domain growth, and domain walls etc., which is helpful to clarify the mechanisms and kinetics of polarization switching, domain growth and ferroelectric fatigue.9,18-20 Especially, the polarization switching and depolarization have been studied by using SPM in the liquid or humid environment. The spatial extent of the electric field created by a biased tip (i.e. tip bias) is controlled by the choice of the medium, resulting in a transition from localized switching dictated by tip radius to uniform 3 ACS Paragon Plus Environment


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switching across the sample.21 Sergei V. Kalinin’s group observed the single-point tip-induced polarization backswitching against the previous external electric field and a surprisingly broad range of domain morphologies in the LiNbO3 single crystal with surface H+ and OH- ions at a humid ambience.19,22,23 The 180o polarization backswitching in microscopic region is the unique routine of depolarization in the single polar ferroelectrics such as LiNbO3. Similarly, triglycine sulfate ((NH2CH2COOH)3·H2SO4, TGS) crystal also has a single polar axis (i.e. b axis) and a mass of surface H+ ions, which are favorable for us to study how to exactly control depolarization and reverse domains.24,25 In this paper, the single tip bias on a (010) TGS crystal can introduce the polarization switching and a new domain in a ~10-m-scale region, and then its polarization backswitching introduces the self-organized ferroelectric domains along c axis. Most importantly, these ordered domains can be well controlled by the voltage and duration of such tip bias. RESULTS AND DISCUSSION The monoclinic TGS crystal shows strong dielectric and ferroelectric anisotropies. The TGS single crystal with edged shapes (Figure 1a) was grown in the saturated solution by a method of the slow evaporation, and then the crystals with (010), (100) and (001) surfaces were prepared and confirmed by the XRD pattern, respectively (Figure S1 in supporting information). The (010) TGS shows the atomic smooth surface with one or two lattice steps, i.e. 1.3 nm or 2.6 nm (Figure 1b). Besides, the relative permittivity (r) of the TGS crystals shows strong anisotropy in Figure 1c. For example, there is a maximum value of r (i.e. ~670) along the b axis at ~50 oC due to ferroelectric-paraelectric transition while the r along the a axis and the c axis is ~9 and ~5 in the range of -196 oC to 80 oC, respectively.26 Furthermore, the monoclinic P21 structure of the TGS crystal just allows a single polar axis, i.e. the b axis, and the saturated polarization (Ps) is ~3.8 μC 4 ACS Paragon Plus Environment

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cm-2 (Figure 1d).24,25 In a word, the TGS crystal shows strong structural, dielectric and ferroelectric anisotropies, which should be an important factor to induce self-organized ferroelectric domains along c axis discussed below.

Figure 1. Surface, dielectric and polarization of the transparent TGS crystal. (a) Optical image of the transparent TGS crystal. (b) Surface topography of the (010) crystal and the height along the dash line. (c) Relative permittivity (r) versus temperature curves along a, b and c axes, where the inset shows the strong anisotropy of r in the ac plane at 25 oC. (d) Polarization versus electric field loop of the (010) TGS crystal.



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A single negative tip bias not only introduces a ~10-m-scale domain through polarization switching but also induces the self-organized granular domains along c axis through polarization backswitching. Here the single negative tip bias is applied for 10 s by a conductive tip (~35 nm diameter) of piezoelectric force microscopy upon the (010) TGS with the homogenous downward polarization. In this process the tip always contacts TGS crystal even after the tip bias is terminated. Figure 2 shows the evolution of ferroelectric domains triggered by the single tip bias. First, a -18 V tip bias switches polarization from downward to upward and then introduces a new ~1.5-m-diameter domain (Figure 2a). Secondly, the -54 V tip bias introduces the upward polarization and a ~4.8-m-diameter domain, and then its 180o polarization backswitching introduces another ~1.1-m-diameter downward domain at the center surface nearest to the tip, i.e. the 1st surface (Figure 2b), where the outer surface underwent polarization switching/backswitching is defined as the 2nd surface. Thirdly, the -90/-126 V tip bias introduces a ~7.7/10.5-m-diameter upward domain, and then its polarization backswitching introduces a ~1.4/2.1-m-diameter downward domain at the 1st surface and some downward granular domains near the upward domain walls (Figure 2c,d). Fourthly, the -144 V tip bias not only introduces a ~12.5-m-diameter upward domain through the first polarization switching, but also allows a ~2.2-m-diameter downward domain at the 1st surface and the self-organized granular domains aligned along c axis and though the tip (i.e. tip-c line) (Figure 2e,f). Besides, the corresponding PFM amplitude images also show the same domain evolution on the tip bias (Figure S2 in supporting information).


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Figure 2. Self-organized domains triggered by a negative tip bias. (a-e) Out-of-plane piezoresponse force microscopy (PFM) phase images after the center position (white dot) of the (010) TGS crystal with downward polarization was polarized by a tip with (a) -18 V, (b) -54 V, (c) -90 V, (d) -126 V and (e) -144 V for 10 s in the 40% humidity ambience, respectively, where the tip bias is applied upon the center point (white dot) that the tip-c line passes through. (f) Amplified image of the red-square region marked in (e). (g-i) Out-of-plane phase images after the TGS was polarized by a tip with (g) -54 V, (h) -90 V and (i) -162 V for 10 s in a 10% humidity ambience, respectively.

Mobile H+ ions at the TGS surface play an important role on the polarization switching and backswitching triggered by a tip bias. The TGS single crystal is transparent and insulated as a result 7 ACS Paragon Plus Environment


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of the band-gap of 5.5 eV at a dry ambience.29 However, such crystal was grown in the saturated solution composed of glycine and sulfuric acids at 30 oC and its surface are favorable for the formation of mobile H+ ions in a humid ambience. This is due to a mass of new H+ in an humid ambience according to the following equation:30 (NH2CH2COOH)3·H2SO4=[(NH2CH2COOH)3·HSO4]-+H+=[(NH2CH2COOH)3·SO4]2-+2H+ The light H+ ions can easily move at the humid TGS surface,19,22,23 while these heavy anions (e.g. [(NH2CH2COOH)3·SO4]2-) hardly move. As a result, the real and imaginary parts of the impedance at the surface of (001) TGS decrease with an ambient humidity increasing, especially at >45% (Figure S3 in supporting information). After some electrons were injected to the TGS crystal under a high negative tip bias, they can attract the light-weight H+ to the 1st surface. As a result, many H+-anion pairs are separated and the immobile anions are excess at the 2nd surface. These negative charges trigger the first polarization switching at both 1st and 2nd surfaces. The injected electrons fast leave through the tip before the H+ ions dispersal after the tip bias suddenly drops to zero, which introduces the polarization backswitching at the 1st surface. This phenomenon also had been reported in the single-polar-axis LiNbO3 crystal.19,27 Since more H+ ions appear at TGS surface in a humid ambience,30 the upward domain introduced by a -54 V or -90 V tip bias at 40% humidity (Figure 2b,c) is much larger than that introduced by the same tip bias at 10% humidity (Figure 2g,h). Even so, the backswitching still introduces a reverse domain at the 1st surface and some self-organized domains along the tip-c line at 10% humidity (Figure 2h,i).


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Figure 3. Stability of self-organized domains along the tip-c line. (a) Phase and (b) amplitude images of the (010) TGS crystal after the PFM tip with -220 V bias stayed at A, B and C for 10 s during its moving from A to C, respectively, where the inset of (a) shows the electric field at A, B and C. (c,d) Amplified amplitude images after the granular domains along the tip-c line were relaxed for (c) 30 minutes and (d) 150 minutes, respectively.

The self-organized granular domains at the 2nd surface are also due to polarization backswitching, however its origin is a little different from the backswitching at the 1st surface. Figure 3a,b show the out-of-plane phase and amplitude images after the (010) TGS crystal had been polarized by the mobile tip, respectively. The tip with -220 V bias located at the dot A for 10 s, moved at 1 m s-1 velocity and then stayed at the dot B for 10 s, then moved to the dot C at the same speed and stayed there for 10 s, and finally the tip was withdrawn from the TGS surface. Since the injected electrons couldn’t leave through the tip with -220 V bias, there is no polarization backswitching at the 1st surface. Even so, the backswitching still occurs and introduces granular 9 ACS Paragon Plus Environment


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domains along the tip-c line. Furthermore, these granular domains due to polarization backswitching are very stable after they are kept in air for 30 and 150 minutes (Figure 3c,d) though they gradually disappear after ~360 minutes partially due to their high domain wall energy (Figure S4 in supporting information). Furthermore, the polarization switching and backswitching can be repeated in the same region of the (010 TGS crystal for 16 cycles by the 180 V bias from the same PFM tip (Figure S5 in supporting information). Since the polarization backswitching occurs at the 2nd surface even if the backswitching does not happen at the 1st surface, the excess heavy anions should be neutralized by H+ ions or positive charges at the 2nd surface which is different from the origin of backswitching at the 1st surface. The granular domains are self-organized along the tip-c line when the negative tip bias is applied in different ways, thus domain nucleation energy (Enuc) may be the lowest along the c axis due to the strong crystal anisotropy. These self-organized domains can be triggered by the -144/-180/-220 V single tip bias upon the (010) TGS crystal in five different ways, i.e. (1) the tip bias with fast increasing/decreasing within 0.02 s and the pulse duration of 5-20 s (Figure 2e and Figure S6 in supporting information), (2) the 10 s tip bias with fast increasing within 0.02 s and slowly decreasing to zero within 45 s to avoid the possible current oscillation through the tip (Figure S7 in supporting information), (3) the 10 s tip bias with increasing/decreasing within 3 s (B dot of Figure 3a), (4) the 10 s tip bias with increasing within 3 s and terminated by withdrawing the tip from the TGS surface within 0.1 s (C dot of Figure 3a), and (5) the 10 s tip bias with fast increasing/decreasing within 0.02 s upon a (010) TGS crystal which was rotated 90o on b axis (Figure S8 in supporting information). Since the polarization backswitching always occurs along the tip-c line, Enuc should have a minimum along c axis. There is strong crystal anisotropy such as the 10 ACS Paragon Plus Environment

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single polar axis and the large difference among the dielectric permittivity of a, b and c axes respectively (Figure 1c and 1d) in TGS crystal, which allows a minimum Enuc along the c axis.

Figure 4. Self-organized domains triggered by a 180 V tip bias. (a) Original out-of-plane PFM phase images of the (010) TGS with upward polarization. Images after the TGS was polarized (b) by a PFM tip with 180 V bias for (b) 5 s and 0 V for 1 minute, and by a PFM tip with 180 V for (c) 5 s, (d) 10 s, (e) 20 s and (f) 50 s and then the tip fast withdraws from the surface, where the insets show the amplitude images of the corresponding regions (white square) in (b-f) respectively.

Furthermore, a high positive tip bias can also introduce the self-organized granular domains through the polarization backswitching along the tip-c line. When a 180 V tip bias is applied on the TGS surface for 5 s and stops instantly, the first polarization switching introduces a ~10-m-scale downward domain, and then the polarization backswitching introduces an upward domain at the 1st surface and a series of ordered granular domains along the tip-c line as well (Figure 4a,b). When the 180 V tip bias is applied on the TGS surface for 5 s and then the tip withdraws from the surface 11 ACS Paragon Plus Environment


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immediately, all domains are similar except for the upward domain at the 1st surface (Figure 4c). With the duration of the 180 V tip bias increasing from 10 s to 50 s, the downward domain becomes bigger and bigger and the upward granular domains are always along the tip-c line (Figure 4d-f). Besides, the PFM amplitude images clearly show self-organized upward domains along the tip-c line, too (Figure S9 in supporting information). The 180o polarization backswitching and the corresponding granular domains along the tip-c line should come from the surface charge change as a result of the interplay among polarization charges, surface movable H+ ions and the strong crystal anisotropy. The electroneutral TGS surface allows mobile H+ ions and immobile anions (e.g. [(NH2CH2COOH)3·SO4]2-) especially at a humid ambience (Figure 5a).30 On one hand, there is surface charge change with time. After high-energy electrons are injected into the 1st surface under a high negative tip bias, a mass of H+ ions are attracted to the 1st surface,19,27 which separates H+-anions pairs and leaves excess immobile anions at the 2nd surface. These negative charge surfaces introduce the first polarization switching and a ~10-m-scale domain. If the tip always contacts the TGS surface and the tip bias suddenly drops to zero, the injected electrons can leave away through the tip and the remaining H+ ions can introduce 180o polarization backswitching and a reverse domain at the 1st surface (Figure 5b).19,27,28,32 In other cases, the injected electrons hardly introduce the polarization backswitching and a reverse domain at the 1st surface (Figure 3 and Figure 5c). On the other hand, there is a surface charge change in space. As mentioned above, the TGS crystal shows strong anisotropic dielectric properties and the single-polar axis (i.e. the b axis). The crystal anisotropy couples with polarization charges and the mobile H+ ions,33,34 and their interplay triggers 180o polarization backswitching along the tip-c line where Enuc has a minimum. Besides, when a high positive tip bias is applied on the TGS surface 12 ACS Paragon Plus Environment

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with upward polarization, some surface electrons leave through the tip and the corresponding holes drive H+ far away from the 1st surface, so there are two positive charge surfaces, i.e. the 1st surface composed of holes and the 2nd surface composed of H+ (Figure 5d). The other physical processes of polarization backswitching along the tip-c line (Figure 5e,f) are similar to those with a high negative tip bias (Figure 5b,c).

Figure 5. Mechanism of the self-organized domains emerges under single tip bias. (a,d) A negative/positive tip bias introduces electrons/holes at the 1st surface, these electrons/holes attract/expel H+ and then results in -q/+q at the 2nd surfaces and the corresponding polarization switching. (b,e) After the tip bias suddenly stops or (c,f) after the tip is fast moved away from the TGS surface, a mass of H+ ions move toward immobile ions and some surface charges are neutralized by space charges, which together with the strong crystal anisotropy induces the polarization backswitching and a series of granular domains along the tip-c line.



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The abnormal polarization backswitching does not appear, when a tip bias is too low or too short, free electrons rather than H+ ions are dominant or polarization charges close to zero at the TGS surface. Neither a -180 V tip bias for 2 s nor a -18 V tip bias for 20-1200 s induces polarization backswitching though they already introduce polarization switching and an m-scale upward domain (Figure S6 and Figure S10 in supporting information). Besides, after a ~1 nm Au film was deposited on the (010) TGS surface, its surface conductivity increases almost ~5 times and thus a -180 V tip bias can introduce the polarization switching and a ~10-m-scale domain even at 5% humidity (Figure S11 in supporting information). However, the polarization backswitching along the tip-c line cannot be induced again since free electrons rather than H+ ions are the majority at TGS surface. Besides, the polarization backswitching does not occur in the (100) or (001) TGS crystals which has no surface polarization charges in theory (Figure S12 in supporting information).35 These results suggest that H+ ions and polarization charges are necessary to the abnormal surface charge change and the corresponding polarization backswitching along the tip-c line in the (010) TGS crystal. CONCLUSIONS The self-organized domains in the ~10-m-scale region can be controlled by a single tip bias in the (010) TGS single crystal. The tip bias introduces the polarization switching and a ~10-m-scale domain, in which the polarization backswitching introduces a reverse domain nearest to the tip and a series of granular reverse domains along the tip-c line. These phenomena are due to the abnormal surface charge change with time and in space as a result of the interplay among polarization charges, mobile H+ ions at surface and the strong crystal anisotropy. This study suggests that the polarization backswitching can be exactly controlled to achieve self-organized domains like the polarization switching along an external electric field, which is helpful to produce novel micro-electronic 14 ACS Paragon Plus Environment

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devices. METHODS Sample preparation. Glycine and diluted sulfuric acid were mixed with 3:1 molecular ratio and stirred for 24 h at 40.0 oC to obtain TGS crystal grains, and then they were further purified by recrystallize twice in ultrapure water. The TGS single crystal was grown in the saturated solution at 30.00.1 oC by slow evaporation. The TGS single crystals with the surface being perpendicular to the a axis, the b axis and the c axis were prepared through cutting crystal along its cleavage plane or through naturally split crystal by heating it unevenly, respectively. Furthermore, Au electrodes were prepared on TGS surfaces for the measurements of macroscopic electric properties. Measurement. The structure and orientation of the TGS single crystal were verified by X-ray diffraction (Bruker D8). Ferroelectric hysteresis loops were measured by a commercial ferroelectric test system (Radiant Multiferroics).The relative dielectric constant (r) and loss were measured by a dielectric tester (Agilent 4294A) in a temperature-controlled chamber (Linkam T95). Furthermore, the morphologies and ferroelectric domains were characterized by a commercial scanning probe microscope (Bruker Multimode 8) with the PFM mode. The PFM experiments are carried out by using a Co/Cr coated conductive tip with 35 nm diameter (MESP-RC, Bruker, USA) and PFM phase/amplitude images are measured with an ac voltage of 25 kHz. A single tip bias is produced from a tip connecting an external amplifier of Bruker or a voltage source (Keithley 2635A) if there is no additional illustration. During PFM measurement, the environment humidity of TGS crystals was controlled by the flux of dry oxygen in a chamber.



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ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. XRD pattern of (010) and (001) TGS crystals; PFM amplitude images of self-organized domains triggered by a negative tip bias; Humidity dependence of surface resistance and impedance; Lifetime, repeatability and emergence conditions of self-organized domains along tip-c axis; PFM amplitude image of self-organized domains triggered by a 180 V tip bias; Domain evolution of the (010) TGS crystal under a -18 V tip bias; Domain evolution of (010) TGS crystal with ~1 nm Au coating layer; Tip-induced polarization switching in (001) and (100) TGS crystals. (PDF) AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (GLY) and [email protected] (JML) ORCID Guoliang Yuan: 0000-0002-0147-7893 Yaojin Wang: 0000-0003-2561-1855 Tom Wu: 0000-0003-0845-4827 Jun-Ming Liu: 0000-0001-8988-8429 Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT The work is supported by the National Key Research Program of China (2016YFA0300101) and the National Natural Science Foundation of China (51790492, 51721001 and 51472118). Besides, G. L. 16 ACS Paragon Plus Environment

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Yuan is supported by the Fundamental Research Funds for the Central Universities (30916011104).



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Self-organized ferroelectric domains controlled by a constant bias from

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