Ferroelectric materials are of interest for such diverse applications as non-volatile Ferroelectric Random Access Memory (FRAM),1) electro-optic modulators2) and frequency converters.3) Especially, LiNbO3 has excellent piezoand pyro-electricity properties, is photo-refractive, and displays nonlinear optical properties. It also has a high spontaneous polarization, 70 μC/cm2, and high Curie temperature, ~1480 K,4,5) so it is suitable for high temperature applications as well. Generally, congruent LiNbO3, which has an R3c structure, is easy to grow under Li deficient conditions. 6,7) However, recent successes using the vapor-transport equilibration (VTE) method8) have enabled the growth of stoichiometric LiNbO3. Although various defect models including those for pseudo-Schottky defects, Schottky defects, and Frenkel defects have been suggested9) to explain energetically preferred defects and defect clusters in congruent LiNbO3, only an Nb antisite, compensated for by four Li ion vacancies9–11) and five Nb antisites compensated for by four Nb vacancies11) were found to successfully explain the stoichiometry of congruent LiNbO3. Atomistic modeling by Donnerberg et al.12) showed that compensation by Nb vacancies is energetically less favorable than compensation by Li vacancies. Recent DFT calculations13) showed that Nb antisite compensated for by Li vacancies, and the Li Frenkel pair, are the most energetically favorable defect clusters in LiNbO3 under Li deficient (congruent) and Li rich (stoichiometric) conditions, respectively. An analysis on various Nb antisite-Li vacancy cluster models determined that several arrangements of Li vacancies around an Nb antisite are nearly energetically equivalent.14)
Interfaces between two opposite polarization domains (Domain walls) are also studied using both experiments and simulations. Gopalan et al.15) suggested two different domain walls, the Y- and X-walls, based on crystallographic orientation; the Y-wall lies parallel to the (112̄0) plane, while the X-wall lies parallel to the (101̄0) plane. In subsequent works,16) the X-wall was identified as a mixed anion-cation plane, while the Y-wall was determined to be alternating planes of cations only and anions only. Energetic studies on the two domain walls17) show that the Y-wall is energetically favored but less mobile. It was also found that non-uniaxial polarization components near the domain walls can lead to Bloch-like characteristics of the X-wall and both Bloch-like and Néel-like characteristics of the Y-walls. 18) Previous studies have demonstrated that defect/domain wall interactions can lead to switching in the preferred orientation of the domain wall from the Y-wall to the X-wall19) or to a reduction of the electric polarization.20) In extending the previous work on defects and domain walls, this study mainly focuses on the interaction between defects and domain walls in LiNbO3 and the effect of those defects on the domain dynamics. Various aspects of defects, including type and charge state, are investigated to understand the effect of domain walls on defect energetics.
Although the ferroelectric fatigue and optical instability of ferroelectric LiNbO3 are known to result from defects/domain wall interactions, these drawbacks still limit the usage of ferroelectric materials. To overcome the current application limits, thorough understanding of the interaction mechanism is necessary. In the current study, the interaction energetics are determined by putting three major point defects
VLi′, Lii· and
NbLi···· at various distances from both the Y-walls and the X-wall. Three major point defects and two distinctive domain walls are identified from previous studies. From the full geometry relaxation, the interaction energetics are determined by looking at the energy difference between the defects near the wall and the defects far away from the wall. Although the size limitation constrains the maximum distance of our study at 6.46 Å for the Y-wall and at 7.75 Å for the X-wall, empirical study with a larger system proves that the defects/domain-wall interactions mainly occur within 5 Å.31) Because the interaction between the defects and the domain wall means that their energies cannot be uniquely separated from each other, we here ascribe the change in the energy of the system to a change in the defect formation energy; we could, with equal merit, ascribe this energy change to a change in the domain wall energy.
provides a schematic view of the Y-wall in LiNbO 3 and the spatial location of each point defect near the Y-wall. As can be seen, the Y-wall sits between two atom planes; point defects are located at different distances from the domain walls. For all cases, the defect/domain wall interactions decreased the energy, indicating that defects are preferentially positioned near the domain wall. For the Y-wall, the quadrupley charged
NbLi···· shows a stronger interaction (~ −0.26 eV), while the singly charged
VLi′ or
Lii· shows weaker interaction (~ −0.12 eV). The singly charged defects are preferentially located at the nearest plane from the Y-wall, while the
NbLi···· prefer to be at the second nearest plane from the wall. For comparison, the energetics of the neutral defects are also considered. Interestingly, three neutral defects show similar energetics regardless of their kinds and the values are quite close to the case of the singly charged defects (
VLix=~-0.11 eV, Liix=~-0.12 eV and
NbLix=~-0.14 eV). Thus, the charge states of defects play an important role in determining the energetics for the defect/Y-wall interactions.
Schematic view of Y-wall and three major points defects in LiNbO3;
Lii·, VLi′ and
NbLi···· are drawn to show spatial location of each point defect around the Y-wall.
A similar study has been also performed for the X-walls. Because our previous study identified two inequivalent X-walls related with the oxygen sublattice, current studies have calculated the interaction energies of intrinsic defects with both the XI-wall and the XII-wall. Although maximum interactions are observed within the second nearest plane from both the X-walls regardless of the charge states of the intrinsic defects, the energetics for their interactions are different. shows a comparison of the maximum defects/X-wall interaction energy within the three nearest planes. As can be seen in , the majority of defects show stronger interaction with the XI-wall than with the XII-wall. The most prominent difference in the interaction energetics is observed for the quadrupley charged
NbLi····. The DFT predicts that the interaction of
NbLi···· with the XI-wall (~ −0.55 eV) will be much stronger than that with the XII-wall (~ − 0.05 eV). For single charged defects, the maximum interaction energies of
Lii· are −0.32 eV for the XI-wall and −0.16 eV for the XII-wall; the maximum interaction energies of
VLi′ are −0.14 eV for the XI-wall and −0.13 eV for the XII-wall. Similar to the fully charged defects, the XI-wall also shows stronger interaction with neutral defects; the value of −0.17 eV of the
NbLix/XI-wall interaction energy is stronger than the value of −0.03 eV of the
NbLix/XII-wall interaction energy. Previous study identified that two inequivalent X-walls have essentially identical values of domain wall energy in a perfect system. With the existence of defects, however, the current study observed that the XI-wall could be energetically more stable than the XII-wall. Thus, the defects/X-walls interactions explain the experimental preference of the XI-wall over the XII-wall.16,19)
Variation of defect formation energy (DFE) as a function of distance from (a) Y-wall, (b) XI-wall and (c) XII-wall. The DFE of three dominant point defects:
Lii· (red),
VLi′ (green) and
NbLi···· (blue) are calculated using density functional theory (DFT).
Previous study has shown that the domain wall in PbTiO332) acts as a trap site for oxygen vacancies. As an extension of that study, the current work shows that the domain wall does not act as a trap site for only oxygen vacancies, but for all other intrinsic defects regardless of their charge states or defect types. For the Y-wall, the quadrupely charged
NbLi···· will more strongly interact with the wall than the singly charged
VLi′ and
Lii·. On the other hand,
Lii·. and
NbLi···· should interact more strongly with the XI-wall than with the XII-wall. Because the strong interaction of
NbLi···· with the domain walls increases the stability of the domain wall, the domain wall motion will be more difficult with the existence of
NbLi····. Thus, among the three intrinsic defects,
NbLi···· will show the strongest pinning effect.
Because the domain walls act as trap sites for defects, defects might form a cluster near the domain walls. In order to verify the energetics of single defect/domain wall interactions, we have also considered defect clusters. For this study, we have considered two different defect pairs,
Lii·+VLi′ and
NbLi····+4VLi′. By assuming that defects do not interact with each other and are equally distant from the wall, we were able to determine the maximum interaction energy of the two defect clusters with one Y-wall and two X-walls; the defect cluster/domain wall interaction energies are shown in the change of DFE from the reference state and listed in . Consistent with the results of the single defect case, three different types of domain walls act as trap sites for both defect pairs. Also, the XI-wall interacts more strongly with both defect clusters.
Comparison of Interaction Energies of Two Defect Complexes with One Y-wall and two X-walls. The DFE at Bulk State is Shown as a Reference for Each Configuration
We have looked at the energetics of the defects interacting with domain walls in LiNbO3. Now we will discuss how the defects can migrate near the domain wall. In order to study the migration of various point defects, we have employed the NEB method along the migration pathway. Because the previous study17) has shown that the Y-wall, lying parallel to the (112̄0) plane, is energetically much more favorable than the two X-walls, our study focused on the migration behavior of defects around the Y-wall. Especially, the current study has focused on the
NbLi····-VLi′ pair, because
NbLi···· is the most highly interacting type of defect and
VLi′ is necessary for mitigating the highly positive charge state of
NbLi····. shows the potential energy profile along the migration pathway of the
NbLi····-VLi′ pair across the Y-wall. The bottom figures show the atomic configuration of the
NbLi····-VLi′ pair across the Y-wall in the initial state (IS), transition state (TS) and final state (FS). As can be seen,
NbLi···· and
VLi′ sit in two oxygen octahedral cages across the Y-wall that are next to each other. Thus, it is reasonable to assume that
NbLi···· will migrate through the shortest pathway to
VLi′, as shown by the cyan arrow in the left bottom of . The migration barrier for
NbLi···· moving toward
VLi′ the site is 3.44 eV at the transition state (TS). This shows that significant energy is required to move
NbLi···· across the Y-wall. Therefore, it is reasonable to think that
NbLi····, which can be easily captured by the Y-wall, will have difficulty migrating across the Y-wall and thus will pin the Y-wall.
Potential energy profile along the migration pathway of the
VLi′/NbLi···· pair across the Y-wall.
We now consider how the migration behavior of the
NbLi····-VLi′ pair changes under surplus electrons. shows the potential energy profile along the migration pathway of the
NbLi····-VLi′ pair under one excess electron.
Potential energy profile along the migration pathway of
V′/NbLi⋯ pair under influence of one extra electron.
The addition of an extra electron decreases the migration barrier of the
NbLi····-VLi′ pair from 3.44 to 3.16 eV. Thus, the extra electron will enhance the migration of
NbLi⋯ into
VLi′. In order to understand the decrease in the migration barrier of
NbLi···· into
VLi′, the electronic density of state (DOS) is analyzed. The inset of shows the site projected DOS at the TS during the migration of
NbLi···· into
VLi′. At the TS,
NbLi···· sits exactly on the Y-wall. (See ) As a result, a defect energy level is created near the conduction band minimum (CBM) of bulk LiNbO3. This energy level created by
NbLi···· is shown in red color in the DOS. We term this energy level a gap state because it is located within the bandgap of bulk LiNbO3. This gap state plays a major role in the change in energy barrier during the migration of
NbLi····. At the IS,
NbLi···· does not yield any defect energy level within the bandgap. On the other hand,
NbLi····, which sits in the Y-wall, will create an additional gap state at the TS. Because this gap state is only available at the TS, extra electrons will go to the bottom of the conduction band at the IS. In contrast, the peeling off of a gap state from the bottom of the conduction band reduces the energy of the system at the TS of the
NbLi····-VLi′ migration. Thus, the migration barrier of the
NbLi····-VLi′ pair is reduced by the addition of an electron. Because
NbLi···· can pin the motion of the Y-wall, the reduction of the migration barrier of
NbLi···· may enhance the movement of the Y-wall by weakening the pinning effect.
References
1. Lim DG, Jang BS, Moon SI, Won CY, Yi J. Characteristics of LiNbO3 Memory Capacitors Fabricated Using a Low Thermal Budget Process. Solid•State Electron 45(7):1159–63.
2001;
2. Macario J, Yao P, Shireen R, Schuetz CA, Shi SY, Prather DW. Development of Electro-Optic Phase Modulator for 94 GHz Imaging System. J Lightwave Technol 27(24):5698–703.
2009;
3. Tehranchi A, Kashyap R. Efficient Wavelength Converters with Flattop Responses Based on Counterpropagating Cascaded SFG and DFG in Low-Loss QPM LiNbO3 Waveguides. Opt Express 17(21):19113–19.
2009;
4. Wong KK. Properties of Lithium Niobate. EMIS Datareviews p. 28. INSPEC, The Institution of Electrical Engineers. United Kingdom, Lon-don: 2002.
5. Volk T, Wöhlecke M. Lithium Niobate: Defects, Photo-refraction and Ferroelectric Switching. Springer Series in MATERIALS SCIENCE p. 115. Springer. Berlin: 2008.
6. Han YH, Smyth DM. Nonstoichiometry and Defects in Linbo3. Am Ceram Soc Bull 62(8):852. 1983;
7. Obryan HM, Gallagher PK, Brandle CD. Congruent Composition and Li-Rich Phase-Boundary of LinbO3. J Am Ceram Soc 68(9):493–96.
1985;
8. Bordui PF, Norwood RG, Jundt DH, Fejer MM. Preparation and Characterization of Off-Congruent Lithium-Niobate Crystals. J Appl Phys 71(2):875–79.
1992;
9. Iyi N, Kitamura K, Izumi F, Yamamoto JK, Hayashi T, Asano H, Kimura S. Comparative-Study of Defect Structures in Lithium-Niobate with Different Compositions. J Solid State Chem 101(2):340–52.
1992;
10. Bollmann W. Stoichiometry And Point-Defects in Lithium-Niobate Crystals. Cryst Res Technol 18(9):1147–49.
1983;
11. Schirmer OF, Thiemann O, Wohlecke M. Defects in linbo3.1. Experimental Aspects. J Phys Chem Solids 52(1):185. 1991;
12. Donnerberg H, Tomlinson SM, Catlow CRA, Schirmer OF. Computer-Simulation Studies of Intrinsic Defects in LinbO3 Crystals. Phys Rev B 40(17):11909. 1989;
13. Xu HX, Lee D, He J, Sinnott SB, Gopalan V, Dierolf V, Phillpot SR. Stability of Intrinsic Defects and Defect Clusters in LiNbO3 from Density Functional Theory Calculations. Phys Rev B 78(17):174103. 2008;
14. Xu HX, Lee D, Sinnott SB, Dierolf V, Gopalan V, Phillpot SR. Structure and Diffusion of Intrinsic Defect Complexes in LiNbO3 from Density Functional Theory Calculations. J Phys: Condens Matter 22(13):135002. 2010;
15. Gopalan V, Dierolf V, Scrymgeour DA. Defect-Domain Wall Interactions in Trigonal Ferroelectrics. Annu Rev Mater Res 37:449–89.
2007;
16. Scrymgeour DA, Gopalan V, Itagi A, Saxena A, Swart PJ. Phenomenological Theory of a Single Domain Wall in Uniaxial Trigonal Ferroelectrics: Lithium Niobate and Lithium Tantalate. Phys Rev B 71(18):184110. 2005;
17. Lee D, Xu H, Dierolf V, Gopalan V, Phillpot SR. Structure and Energetics of Ferroelectric Domain Walls in LiNbO3 from Atomic-level Simulations. Phys Rev B 82(1):014104. 2010;
18. Lee D, Behera RK, Wu P, Xu HX, Sinnott SB, Phillpot SR, Chen LQ, Gopalan V. Mixed Bloch-Néel-Ising Character of 180° Ferroelectric Domain Walls. Phys Rev B 80(6):060102(R). 2009;
19. Lee D, Xu H, Dierolf V, Gopalan V, Phillpot SR. Shape of Ferroelectric Domains in LiNbO3 and LiTaO3 from Defect/Domain-Wall Interactions. Appl Phys Lett 98(9):092903. 2011;
20. Stone G, Lee D, Xu H, Phillpot SR, Dierolf V. Local Probing of the Interaction between Intrinsic Defects and Ferroelectric Domain Walls in Lithium Niobate. Appl Phys Lett 102(4):042905. 2013;
21. Kohn W, Sham LJ. Self-Consistent Equations Including Exchange And Correlation Effects. Phys Rev 140(4A):A1133. 1965;
22. Perdew JP, Yue W. Accurate and Simple Density Functional For The Electronic Exchange Energy - Generalized Gradient Approximation. Phys Rev B 33(12):8800. 1986;
23. Monkhorst HJ, Pack JD. Special Points for Brillouin- Zone Integrations. Phys Rev B 13(12):5188. 1976;
24. Kresse G, Furthmuller J. Efficiency of ab-initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set. Comput Mater Sci 6(1):15–50.
1996;
25. Kresse G, Furthmuller J. Efficient Iterative Schemes for ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys Rev B 54(16):11169. 1996;
26. Blochl PE. Projector Augmented-Wave Method. Phys Rev B 50(24):17953. 1994;
27. Li QK, Wang B, Woo CH, Wang H, Wang R. First-Principles Study on the Formation Energies of Intrinsic Defects in LiNbO3. J Phys Chem Solids 68(7):1336–40.
2007;
28. Pulay P. Convergence Acceleration Of Iterative Sequences - The Case Of Scf Iteration. Chem Phys Lett 73(2):393–98.
1980;
29. Jónsson H, Mills G, Jacobsen KW. Nudged Elastic Band Method for Finding Minimum Energy Paths of Transitions. CLASSICAL AND QUAN-TUM DYNAMICS IN CONDENSED PHASE SIMULATIONS p. 385. World Scientific; 1998.
30. Henkelman G, Uberuaga BP, Jonsson H. A Climbing Image Nudged Elastic Band Method for Finding Saddle Points and Minimum Energy Paths. J Chem Phys 113(22):9901–4.
2000;
31. Lee D. Structure and dynamics of interfaces in organic and inorganic materials using atomic level simulation (in English). 111. PhD Thesis University of Florida; Gainesville, Fl: 2010.
32. He L, Vanderbilt D. First-Principles Study of Oxygen-Vacancy Pinning of Domain Walls in PbTiO3. Phys Rev B 68(13):134103. 2003;