Increased optical damage resistance of Zr:LiNbO<sub>3</sub> crystals

Sun, L.; Guo, Fengyun; Lv, Qiang; Yu, Hongwei; Li, Hongtao; Wei, Caihong; Xu, Youlong; Zhao, Liancheng

doi:10.1002/crat.200710935

Cited by 31 publications

(9 citation statements)

References 16 publications

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“…From the analysis above, we found that the ZrO 2 doping threshold concentration is less than that previously reported [11,12]. A conclusion can be drawn that the ZrO 2 doping threshold concentration decreases as the ratio of [Li]/[Nb] increases.…”

Section: Resultscontrasting

confidence: 43%

“…However, there still exist two drawbacks, namely the long response time and the low optical damage resistance. Therefore Fe:LiNbO 3 has been doped with optical damage resistant impurities (ODRI), such as Mg, Zn, In, Sc, Hf, and Zr [6][7][8][9][10][11][12][13][14]. As a result, fast response speed and high optical damage resistance ability (ODRA) have been achieved in ODRI-doped Fe:LiNbO 3 crystals.…”

Section: Introductionmentioning

confidence: 99%

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Growth and spectroscopic characterization of Zr:Fe:LiNbO3 crystals with various Li/Nb ratios

Fan

Xia

et al. 2010

Journal of Crystal Growth

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Section: Resultscontrasting

confidence: 43%

Section: Introductionmentioning

confidence: 99%

Growth and spectroscopic characterization of Zr:Fe:LiNbO3 crystals with various Li/Nb ratios

Fan

Xia

et al. 2010

Journal of Crystal Growth

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“…[93][94][95][96][97][98] The properties of LN doped with optical damage resistant ions were first summarized in a review paper 10 and later in a book by Volk et al 99 Recently, Kong et al 100 reviewed advances in the photorefraction of doped LN, focusing on tetra-, penta-, and hexavalent ions, including doubly-and even triply-doped crystals. They concluded that LN triply doped by Zr, Fe, and Mn shows excellent non-volatile holographic storage properties, and V and Mo single-doped LN have fast response and multi-wavelength storage characteristics.…”

Section: Other Divalent Trivalent and Tetravalent Odr Dopantsmentioning

confidence: 99%

“…44,45,47 In addition, the increase in the valence of the dopant decreases the threshold. [94][95][96][97][98] In general, the incorporation of ODR ions reduces the amount of antisite Nb Li in the lattice. In nearly stoichiometric LN crystals where the Nb Li concentration is almost zero, the threshold value of the dopant concentration can be lower than 0.2 mol.…”

Section: Other Divalent Trivalent and Tetravalent Odr Dopantsmentioning

confidence: 99%

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

Lengyel

Péter

Kovács

et al. 2015

Applied Physics Reviews

104

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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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“…The optical damage resistance of LN crystals can be improved by doping with certain divalent, trivalent, or tetravalent cations (e.g., Mg 2 , Zn 2 , In 3 , Sc 3 , Hf 4 ) above a critical amount [1]. Increased damage resistance in the visible optical range has been reported recently in tetravalent Zr- [2,3] and Sn-doped [4] LN crystals as well. Ferroelectric domain engineering with auxiliary UV light is of growing interest in damage-resistant lithium niobate [5].…”

mentioning

confidence: 99%

Photorefractive damage resistance threshold in stoichiometric LiNbO_3:Zr crystals

et al. 2013

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Several optical methods including ultraviolet absorption, infrared absorption of the hydroxyl ions, Raman spectroscopy, and the Z-scan method have been used to determine the damage resistance threshold in 0-0.72 mol. % Zr-containing, flux-grown, nearly stoichiometric LiNbO 3 single crystals. All spectroscopical methods used indicate that samples containing at least ≈0.085 mol: % Zr in the crystal are above the threshold while Z-scan data locate the photorefractive damage threshold between 0.085 and 0.314 mol. % Zr. For LN grown from congruent melt the threshold concentration of the optical damage resistant (ODR) ions is roughly 5, 4, and 2 mol. % for di-, tri-, and tetravalent ions, respectively. For example, the threshold concentration for Zr-doped congruent LN crystals was found to be at about 2 mol. % [3,10,11]. Another factor beside the ODR ions and their valency strongly effecting the threshold concentration is stoichiometry of the crystal. The incorporation of ODR ions reduces the amount of antisite Nb Li in the lattice. In nearly stoichiometric LiNbO 3 (sLN) crystals where the Nb Li concentration is almost zero, the threshold value of the dopant concentration can be lower than 0.2 mol. % as was observed for Mg-doped sLN [12] used for instance for terahertz pulse generation [13]. Zr-doped nearly stoichiometric LN crystals prepared by the vapor transport equilibration method were found to have high resistance against optical damage when doped above 0.5 mol. % Zr [14]. The basic advantage of choosing tetravalent ODR dopants comes from their lower damage threshold concentrations; lower built-in dopant content facilitates the growth of more homogeneous crystals, resulting in high-quality samples for device applications.The aim of the present work is to characterize the damage resistance properties of tetravalent Zr-doped sLN crystals by ultraviolet (UV), infrared (IR), and Raman spectroscopies as well as by the Z-scan method. These methods proved earlier very efficient to determine the threshold concentration of the dopants.A series of stoichiometric LN crystals doped with Zr in the 0-0.45 mol. % concentration range were grown by the high-temperature top-seeded solution growth method using K 2 O flux [12]. The Zr concentration in the crystal was determined by inductively coupled plasma mass spectroscopy (ICP-MS). As shown in Fig. 1, the amount of incorporated Zr, at least in the range 0-0.715 mol. % realized in our samples, monotonously increases with increasing concentration of Zr in the starting flux. The relatively high distribution coefficient of Zr as compared to that observed in the melt-grown congruent crystals [3] may be related to the different growing technique, similarly to the case of Mg [12].For optical spectroscopical measurements 1-2 mm thick z-and y-cut samples have been prepared. The UV-visible absorption spectra of z-cut sLN:Zr crystals were measured by a Jasco V-550 spectrometer at room temperature. The spectra of the stretching vibrational bands of the hydroxyl ions (OH − ) in sLN:Zr were

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Increased optical damage resistance of Zr:LiNbO₃ crystals

Cited by 31 publications

References 16 publications

Growth and spectroscopic characterization of Zr:Fe:LiNbO3 crystals with various Li/Nb ratios

Growth and spectroscopic characterization of Zr:Fe:LiNbO3 crystals with various Li/Nb ratios

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

Photorefractive damage resistance threshold in stoichiometric LiNbO_3:Zr crystals

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Increased optical damage resistance of Zr:LiNbO3 crystals

Cited by 31 publications

References 16 publications

Growth and spectroscopic characterization of Zr:Fe:LiNbO3 crystals with various Li/Nb ratios

Growth and spectroscopic characterization of Zr:Fe:LiNbO3 crystals with various Li/Nb ratios

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

Photorefractive damage resistance threshold in stoichiometric LiNbO_3:Zr crystals

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Increased optical damage resistance of Zr:LiNbO₃ crystals