Subsolidus phase relations and the crystallization region of LiNbO3 in the system Li2O–B2O3–Nb2O5

Huang, Can; Wang, Shichao; Ye, Ning

doi:10.1016/j.jallcom.2010.04.146

Cited by 17 publications

(8 citation statements)

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“…Kondo,18 Hemmerling and Hergt, 19 and Hibiya 20 reported the Li 2 O-V 2 O 5 mixture to be a suitable solvent both for liquid phase epitaxy and bulk flux growth of sLN crystals. Recently, Huang et al 21 identified the crystallization region of LN in the B 2 O 3 -Li 2 O-Nb 2 O 5 ternary system. Despite the lower critical crystallization temperatures below 1170 C for all these growth experiments, the results of the composition measurements were not fully satisfactory as the solvent components (V, B, W ions) were also incorporated into the crystals (Voronkova reported built-in concentrations of 3-5 at.…”

Section: Growth Of Stoichiometric Linbo 3 a Early Workmentioning

confidence: 99%

Growth, defect structure, and THz application of stoichiometric lithium niobate

Lengyel

Péter

Kovács

et al. 2015

Applied Physics Reviews

105

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Owing to the extraordinary richness of its physical properties, congruent lithium niobate has attracted multidecade-long interest both for fundamental science and applications. The combination of ferro-, pyro-, and piezoelectric properties with large electro-optic, acousto-optic, and photoelastic coefficients as well as the strong photorefractive and photovoltaic effects offers a great potential for applications in modern optics. To provide powerful optical components in high energy laser applications, tailoring of key material parameters, especially stoichiometry, is required. This paper reviews the state of the art of growing large stoichiometric LiNbO 3 (sLN) crystals, in particular, the defect engineering of pure and doped sLN with emphasis on optical damage resistant (ODR) dopants (e.g., Mg, Zn, In, Sc, Hf, Zr, Sn). The discussion is focused on crystals grown by the high temperature top seeded solution growth (HTTSSG) technique using alkali oxide fluxing agents. Based on high-temperature phase equilibria studies of the Li 2 O-Nb 2 O 5 -X 2 O ternary systems (X ¼ Na, K, Rb, Cs), the impact of alkali homologue additives on the stoichiometry of the lithium niobate phase will be analyzed, together with a summary of the ultraviolet, infrared, and far-infrared absorption spectroscopic methods developed to characterize the composition of the crystals. It will be shown that using HTTSSG from K 2 O containing flux, crystals closest to the stoichiometric composition can be grown characterized by a UV-edge position of at about 302 nm and a single narrow hydroxyl band in the IR with a linewidth of less than 3 cm À1 at 300 K. The threshold concentrations for ODR dopants depend on crystal stoichiometry and the valence of the dopants; Raman spectra, hydroxyl vibration spectra, and Z-scan measurements prove to be useful to distinguish crystals below and above the photorefractive threshold. Crystals just above the threshold are preferred for most nonlinear optical applications apart holography and have the additional advantage to minimize the absorption even in the far-infrared (THz) range. The review also provides a discussion on the progress made in the characterization of non-stoichiometry related intrinsic and extrinsic defect structures in doped LN crystals, with emphasis on ODR-ion-doped and/or closely stoichiometric systems, based on both spectroscopic measurements and theoretical modelling, including the results of first principles quantum mechanical calculations on hydroxyl defects. It will also be shown that new perspective applications, e.g., the generation of high energy THz pulses with energies on the tens-of-mJ scale, are feasible with ODR-doped sLN crystals if optimal conditions, including the contact grating technique, are applied. V C 2015 AIP Publishing LLC.

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Section: Growth Of Stoichiometric Linbo 3 a Early Workmentioning

confidence: 99%

Growth, defect structure, and THz application of stoichiometric lithium niobate

Lengyel

Péter

Kovács

et al. 2015

Applied Physics Reviews

105

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“…Single crystals of the Li 2 O-B 2 O 3 system are of considerable interest for their practical applications. Due to its good dissolvability, low melting temperature and resistance against transition metal contamination, lithium metaborate (LMB) LiBO 2 is widely employed as a flux or solvent [62]. It is an excellent basic flux for silicate analysis [63], for the synthesis of low-density γ -Al 2 O 3 from high-density α-Al 2 O 3 [64], for the identification and characterization of resistant minerals containing uranium and thorium [65] and for the growth of single crystals [66][67][68].…”

Section: General Overviewmentioning

confidence: 99%

The ionic conductivity in lithium-boron oxide materials and its relation to structural, electronic and defect properties: insights from theory

Islam

Bredow

Heitjans

2012

J. Phys.: Condens. Matter

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We review recent theoretical studies on ion diffusion in (Li(2)O)(x)(B(2)O(3))(1-x) compounds and at the interfaces of Li(2)O :B(2)O(3) nanocomposite. The investigations were performed theoretically using DFT and HF/DFT hybrid methods with VASP and CRYSTAL codes. For the pure compound B(2)O(3), it was theoretically confirmed that the low-pressure phase B(2)O(3)-I has space group P3(1)21. For the first time, the structure, stability and electronic properties of various low-index surfaces of trigonal B(2)O(3)-I were investigated at the same theoretical level. The (101) surface is the most stable among the considered surfaces. Ionic conductivity was investigated systematically in Li(2)O, LiBO(2), and Li(2)B(4)O(7) solids and in Li(2)O:B(2)O(3) nanocomposites by calculating the activation energy (E(A)) for cation diffusion. The Li(+) ion migrates in an almost straight line in Li(2)O bulk whereas it moves in a zig-zag pathway along a direction parallel to the surface plane in Li(2)O surfaces. For LiBO(2), the migration along the c direction (E(A) = 0.55 eV) is slightly less preferable than that in the xy plane (E(A) = 0.43-0.54 eV). In Li(2)B(4)O(7), the Li(+) ion migrates through the large triangular faces of the two nearest oxygen five-vertex polyhedra facing each other where E(A) is in the range of 0.27-0.37 eV. A two-dimensional model system of the Li(2)O :B(2)O(3) interface region was created by the combination of supercells of the Li(2)O (111) surface and the B(2)O(3) (001) surface. It was found that the interface region of the Li(2)O:B(2)O(3) nanocomposite is more defective than Li(2)O bulk, which facilitates the conductivity in this region. In addition, the activation energy (E(A )) for local hopping processes is smaller in the Li(2)O :B(2)O(3) nanocomposite compared to the Li(2)O bulk. This confirms that the Li(2)O:B(2)O(3) nanocomposite shows enhanced conductivity along the phase boundary compared to that in the nanocrystalline Li(2)O.

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“…In recent years, lithium metaborate (LMB) LiBO 2 has drawn considerable interest because of its technical applications. Because of its good dissolvability, low melting temperature, and the resistance against transition-metal contamination, LMB is widely employed as a flux or solvent . It is an excellent basic flux for silicate analysis, for the synthesis of low-density γ-Al 2 O 3 from high-density α-Al 2 O 3 , for the identification and characterization of resistant minerals containing uranium and thorium, and for the growths of single crystals. − LMB is also used as a chemical modifier during the mechano-chemical synthesis processes for generating new compounds from clays and refractory materials .…”

Section: Introductionmentioning

confidence: 99%

Formation and Mobility of Li Point Defects in LiBO₂: A First-Principles Investigation

2011

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Subsolidus phase relations and the crystallization region of LiNbO3 in the system Li2O–B2O3–Nb2O5

Cited by 17 publications

References 25 publications

Growth, defect structure, and THz application of stoichiometric lithium niobate

Growth, defect structure, and THz application of stoichiometric lithium niobate

The ionic conductivity in lithium-boron oxide materials and its relation to structural, electronic and defect properties: insights from theory

Formation and Mobility of Li Point Defects in LiBO₂: A First-Principles Investigation

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Subsolidus phase relations and the crystallization region of LiNbO3 in the system Li2O–B2O3–Nb2O5

Cited by 17 publications

References 25 publications

Growth, defect structure, and THz application of stoichiometric lithium niobate

Growth, defect structure, and THz application of stoichiometric lithium niobate

The ionic conductivity in lithium-boron oxide materials and its relation to structural, electronic and defect properties: insights from theory

Formation and Mobility of Li Point Defects in LiBO2: A First-Principles Investigation

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Formation and Mobility of Li Point Defects in LiBO₂: A First-Principles Investigation