scholarly journals Исследование структурного совершенства монокристаллов ниобата лития разного состава и генезиса методом ИК спектроскопии в области валентных колебаний водородных связей

2022 ◽  
Vol 130 (1) ◽  
pp. 160
Author(s):  
Л.А. Бобрева ◽  
Н.В. Сидоров ◽  
Н.А. Теплякова ◽  
М.Н. Палатников ◽  
С.А. Климин ◽  
...  

We have analyzed complex defects due to the presence of hydrogen bonds in the crystal structure in nominally pure lithium niobate crystals with different Li/Nb ratio, in crystals alloyed with magnesium and zinc in a wide concentration range (LiNbO3 : Mg (0.19-5.91 mol.% MgO) and LiNbO3 : Zn (0.04-6.5 mol. % ZnO)) and in the double-alloyed crystals (LiNbO3 : Y(0.24) : Mg(0.63 wt. %) and LiNbO3 : Gd (0.25) : Mg(0.75 wt. %)), obtained by technology of direct melt alloying, and also in the double-alloyed crystal (LiNbO3 : Mg(5. 05 mol.% MgO) : Fe(0.009 mol.% Fe2O3)) grown from a charge synthesized using the technology of homogeneous alloying with magnesium and iron Nb2O5. We revealed the influence of doping impurities on the concentration of OH-groups, the type and localization of complex defects in the crystal structure. The change in the number of hydrogen atom positions in the structure of the LiNbO3 crystal allow us to judge with sufficient accuracy whether the crystal composition is stoichiometric or congruent. For doped crystals of different compositions data were obtained testifying to changes in the character of complexation of OH-groups with point defects of the cationic sublattice with formation of defects: MеLi-OH-, MеLi-MеNb-OН. A change in the mechanism of entry of the dopant cation into the structure dramatically affects the change in the properties of the crystal.The difference in the frequencies (and, correspondingly, in the values of the quasi-elastic constants of the O-H bonds) in the spectrum of a congruent crystal and doped crystals can also be contributed by differences in the electronegativity and ionic radii of the principal and doping cations.

Author(s):  
Наталья Александровна Теплякова ◽  
Николай Васильевич Сидоров ◽  
Михаил Николаевич Палатников

Исследованы ИК-спектры поглощения в области валентных колебаний OH - групп кристаллов ниобата лития стехиометрического и конгруэнтного составов. Рассчитана концентрация OH - групп, отношение Li / Nb, а также концентрация точечных дефектов Nb и V. Результаты расчетов совпадают с литературными данными и подтверждаются фазовой диаграммой ниобата лития. Показано, что увеличение количества свободных протонов (вносящих вклад в проводимость) может обуславливать более высокие электропроводность, скорость термической фиксации голограмм и снижение эффекта фоторефракции. The IR absorption spectra in the region of stretching vibrations of OH - groups of lithium niobate crystals of stoichiometric and congruent compositions are studied. The results of calculations of the OH - groups concentration, the Li / Nb ratio and the concentration of point defects Nb and V coincide with the literature data. The phase diagram of lithium niobate confirms these results. It is shown that an increase in the number of free protons that contribute to conductivity can lead to reducing the optical damage and higher electrical conductivity and the rate of thermal fixation of holograms.


2020 ◽  
Vol 11 (3-2020) ◽  
pp. 173-177
Author(s):  
M. V. Smirnov ◽  
◽  
N. V. Sidorov ◽  
N. A. Teplyakova ◽  
V. B. Pikulev ◽  
...  

The photoluminescence intensity in lithium niobate crystals close to the stoichiometric composition being lower than in a congruent crystal was established. The increase of Li / Nb ratio leads to shifting the photoluminescence bands to the short-wavelength region of the spectrum and changing the fundamental absorption edge of the crystals under study. It was shown that, in addition to point defects in the cationic sublattice, complex defects due to the presence of OH groups and compensation defects (VLi / VNb) in the structure can also contribute to photoluminescence.


2021 ◽  
Vol 91 (1) ◽  
pp. 64
Author(s):  
Р.А. Титов ◽  
В.М. Воскресенский ◽  
Н.В. Сидоров ◽  
Н.А. Теплякова ◽  
М.Н. Палатников

It is shown that the use of B2O3 as a flux allows us to obtain the nominally pure LiNbO3 crystals possessing high compositionally uniformity. The LiNbO3:B crystals have both the increased ordering of the structural units of the cation sublattice, close to stoichiometric crystals, and high optical damage resistance. According to the results of computer simulation it was found that the boron element can incorporate into the faces of oxygen tetrahedra of the LiNbO3 crystal structure. Trace amounts of boron (10⋅10-4 wt. %) in the LiNbO3:B structure prevent the formation of the point defects (NbLi). At the same time, B3+ noticeably deforms the oxygen sublattice of the LiNbO3 crystal structure thereby it changes the polarizability of the oxygen octahedra, which determines the nonlinear optical properties of the crystal.


2020 ◽  
Vol 128 (5) ◽  
pp. 643
Author(s):  
Н.В. Сидоров ◽  
М.В. Смирнов ◽  
Н.А. Теплякова ◽  
М.Н. Палатников

Photoluminescence was studied in the volume of congruent and near-stoichiometric lithium niobate crystals obtained by different technologies. Luminescence intensity in near-stoichiometric crystals was found to be lower than that in a congruent crystal. We have shown that not only basic centers (caused by point defects NbLi, VLi) contribute to luminescence, but also complex defects caused by existence of OH-groups.


2020 ◽  
Vol 312 ◽  
pp. 121-127
Author(s):  
Maxim Smirnov ◽  
Nikolay V. Sidorov ◽  
Natalya A. Teplyakova ◽  
Mikhail Palatnikov ◽  
Alexander Vjacheslavovich Syuy

The photoluminescence intensity in lithium niobate crystals close to the stoichiometric composition is lower than in a congruent crystal was established. An increase in the Li / Nb ratio leads to a shift in the photoluminescence bands to the short-wavelength region of the spectrum and a change in the fundamental absorption edge of the crystals under study. It was shown that, in addition to point defects in the cationic sublattice, complex defects due to the presence of OH groups in the structure can also contribute to photoluminescence.


Author(s):  
Николай Васильевич Сидоров ◽  
Наталья Александровна Теплякова ◽  
Михаил Николаевич Палатников

Методом ИК-спектроскопии в области валентных колебаний OH - групп выполнен анализ комплексных дефектов, обусловленных наличием в структуре кристалла водородных связей, в номинально чистых кристаллах ниобата лития конгруэнтного и стехиометрического состава с разным отношением Li / Nb, а также в кристаллах LiNbO: Zn(0,04 - 6,5 мол.% ZnO), легированных цинком в широком диапазоне концентраций, полученным по технологии прямого легирования расплава. Выявлено влияние легирующих примесей на концентрацию OH - групп, вид и локализацию комплексных дефектов в структуре кристалла. Показано, что изменение количества позиций атомов водорода в структуре кристалла LiNbO позволяет с достаточной точностью судить о соответствии его состава стехиометрическому или конгруэнтному составу. Для легированных кристаллов LiNbO : Zn(0,04 - 6,5 мол.% ZnO) получены данные, свидетельствующие об изменении при прохождении концентрационных порогов характера комплексообразования OH - групп с точечными дефектами катионной подрешетки. При этом, вследствие изменения механизма вхождения легирующего катиона в структуру кардинально изменяются свойства кристалла. Вклад в различие частот (и, соответственно, в значение квазиупругих постоянных связей OH -) в спектре конгруэнтного кристалла и легированных кристаллов может вносить также различие электроотрицательностей и ионных радиусов основных и легирующих катионов. An analysis of complex defects was carried out by IR-spectroscopy method in the area of OH - groups stretching vibrations. The defects are caused by hydrogen bonds present in the structure of nominally pure congruent lithium niobate crystals, crystals of stoichiometric composition with a different Li / Nb ratio, as well as in LiNbO: Zn(0,04 - 6,5 мол.% ZnO) crystals doped in a wide range of concentrations due to direct doping of the melt method. Dopants were determined to influence OH - groups concentration, type and localization of complex defects in the crystals structure. A change in the amount of hydrogen sites in the LiNbO crystals structure was shown to evaluate the composition either stoichiometric or congruent. The character of OH - groups complexing with cation sublattice point defects was shown to change when doped crystals LiNbO: Zn(0,04 - 6,5 мол.% ZnO) trespass concentration thresholds. Dopant incorporation mechanism changes at this drastically, thus crystal properties also change quite sharply. Frequencies (as well as quasi-elastic constants of OH - bonds) change in congruent and doped crystals due to a difference in electronegativities and ionic radii of the main and dopant cations.


2020 ◽  
Vol 11 (3-2020) ◽  
pp. 38-43
Author(s):  
А. A. Gabain ◽  

The analysis of structural particularities of nominally pure and doped LiNbO3single crystals was performed by methods of Raman light scattering and infrared absorption. The concentration of OH groups, as well as the concentration of point defects is calculated from IR absorption spectra in the region of stretching vibrations of OH groups. A correlation has been determined in behavior of IR absorption spectra bands of strongly doped LiNbO3:Zn crystals with the behavior of the Raman spectra band that correspondsto stretching bridge vibrations of oxygen atoms in octahedra along the polar axis.


Author(s):  
Galina M. Kuz’micheva ◽  
Liudmila. I. Ivleva ◽  
Irina A. Kaurova ◽  
Evgeny V. Khramov ◽  
Victor B. Rybakov ◽  
...  

Crystals ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 458
Author(s):  
Nikolay V. Sidorov ◽  
Natalia A. Teplyakova ◽  
Olga V. Makarova ◽  
Mikhail N. Palatnikov ◽  
Roman A. Titov ◽  
...  

Defect structure of nominally pure lithium niobate crystals grown from a boron doped charge have been studied by Raman and optical spectroscopy, laser conoscopy, and photoinduced light scattering. An influence of boron dopant on optical uniformity, photoelectrical fields values, and band gap have been also studied by these methods in LiNbO3 crystals. Despite a high concentration of boron in the charge (up to 2 mol%), content in the crystal does not exceed 10−4 wt%. We have calculated that boron incorporates only into tetrahedral voids of crystal structure as a part of groups [BO3]3−, which changes O–O bonds lengths in O6 octahedra. At this oxygen–metal clusters MeO6 (Me: Li, Nb) change their polarizability. The clusters determine optically nonlinear and ferroelectric properties of a crystal. Chemical interactions in the system Li2O–Nb2O5–B2O3 have been considered. Boron, being an active element, structures lithium niobate melt, which significantly influences defect structure and physical properties of a crystal grown from such a melt. At the same time, amount of defects NbLi and concentration of OH groups in LiNbO3:B is close to that in stoichiometric crystals; photorefractive effect, optical, and compositional uniformity on the contrary is higher.


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