Growth and Optical Spectra of Zn∶Er∶LiNbO_3 Crystals Using Bridgman Method

The growth of LiNbO3 single crystal with Er^3＋ and Zn^2＋ co-doped using Bridgman method and its characteristic absorption spectra and fluorescence spectra were reported. Large-size crystals initially containing Zn^2＋ （3%） and Er^3＋ （0.6%） with good optical quality were obtained using optimized conditions such as a growth rate of 0.8- 1.5 mm·h^-1 and a temperature gradient of about 30 - 35℃·cm^-1 across the solid-liquid interface and the sealed platinum crucible. X-ray diffraction and differential thermal analysis （DTA） were used to characterize the crystals. The results indicate that the concentration of Er^3＋ ions in crystals, their absorption intensity, and their fluorescence intensity decrease from the bottom to the top in the crystals. However, for the upper part of the crystal, the up-conversion fluorescence intensity is higher than that of the lower part excited by an 800 or 970 nm pump. The effects of the crystal lattice, their structural defect and their effective segregation of Er^3＋ ions were discussed with respect to the variations of the up-conversion fluorescence intensity.

Improvement of photorefractive properties in Hf:Fe:LiNbO_3 crystals with various [Li]/[Nb] ratios

Photorefractive properties of Hf：Fe：LiNbO3 crystals with various [Li]/[Nb] ratios have been investigated at 488 nm wavelength based on the two-wave coupling experiment. High diffraction efficiency and large recording sensitivity are observed and explained. The decrease in Li vacancies is suggested to be the main contributor to the increase in the photoconductivity and subsequently to the induction of the improvement of recording sensitivity. The saturation diffraction efficiency is measured up to 80.2%, and simultaneously the recording sensitivity of 0.91 cm/J is achieved to in the Hf：Fe：LiNbO3 crystal grown from the melt with the [Li]/[Nb] ratio of 1.20, which is significantly enhanced as compared with those of the Hf：Fe：LiNbO3 crystal with the [Li]/[Nb] ratio of 0.94 in melt under the same experimental conditions. Experimental results definitely show that increasing the [Li]/[Nb] ratio in crystal is an effective method＇for Hf：Fe：LiNbO3 crystal to improve its photorefractive properties.

Transmission Spectral Characteristics of Photonic Crystals Milled in Annealed Proton-Exchange LiNbO_3 Waveguide

Transmission spectra of triangular lattice photonic crystals milled in the top surface of an annealed proton- exchange waveguide are numerically simulated. The effects of the finite depth, conical shape, trapezoidal shape and hybrid shape of holes are theoretically analyzed. Due to the difficulty of milling high aspect-ratio cylindrical holes in lithium niobate （LiNbO3 ）, a compromised solution is proposed to improve the overlap between shallow holes and the waveguide mode, and useful transmission spectra with strong contrast and sharp band edges are achieved.

Growth and Optical Spectra of Zn∶Er∶LiNbO_3 Crystals by Bridgman Method

The growth of LiNbO3 single crystal with Er^3＋/Zn^2＋ co-doped by the bridgman method and the characteristics of absorption spectra and fluorescence spectra were reported. By means of the optimized con- ditions such as growth rate of 0.8 - 1.5 mm · h^- 1, temperature gradient about 30 - 35℃ ·cm^-1 across the solid-liquid interface and sealed platinum, large size crystals containing Zn^2＋ （3%） and Er^3＋ （0.6%） with good optical quality were obtained. X-ray diffraction and DTA were used to characterize the crystals. The results indicate that the concentration of Er^3＋ ions in crystals decrease along the growth direction, the absorption intensity and the fluorescence intensity ions also decrease along the growth direction. of Er^3＋ However, for the upper part crystal, the upconversion fluorescence intensity is higher than that of the lower part crystal excited with 800 or 970 nm pump. The effects of crystal lattice, structure defect and effective segregation of Er^3＋ ions were discussed in respect to the variations were discussed of upconversion fluorescence intensity.

Influence of Oxidation and Reduction Treatments on the Photorefractive Properties of Mg:In:Fe:LiNbO_3 Crystals

A series of Mg：In：Fe：LiNbO3 crystals were grown by Czochralski technique; their absorption spectra and photo scattering resistance ability after oxidation or reduction treatment were measured by light spot distortion method, and their response time and exponential gain coefficient were tested by two-beam coupling experiment. Besides, the effective carrier concentration has been calculated. The results showed that the absorption edges of reduced and oxidized crystals are respectively shifted to violet and Einstein compared with those of the growth state crystal. From oxidation state to growth state to reduction state of the samples, the photo scattering resistance ability and response time decrease while the exponential gain coefficient and concentration of effective carriers increase. The reduction treatment was necessary for the Mg：In：Fe：LiNbO3 crystals to enhance their photorefractive properties.

Effect of Hf^(4+) doping on structure and enhancement of upconversion luminescence in Yb:Tm:LiNbO_3 crystals

A series of Yb：Tm：LiNbO_3 crystals doped with x mol% Hf^（4＋）ions（x = 2, 4, and 6） were grown by the Czochralski method. The dopant occupancy and defect structure of Hf：Yb：Tm：LiNbO_3 crystals were investigated by x-ray diffraction and infrared transmission spectra. The influence of Hf^（4＋）ions concentration on UV–VIS–NIR absorption spectra of Hf：Yb：Tm：LiNbO_3 crystals was discussed. The upconversion luminescence of Hf：Yb：Tm：LiNbO_3 crystals was obtained under 980 nm excitation. Strong emissions were observed at 475 nm in the blue wavelength range and 651 nm in the red wavelength range. Remarkably, enhancement of the red and blue upconversion luminescence was achieved by tridoping Hf^（4＋）ions.

Ultraviolet laser-induced photovoltaic effects in miscut ferroelectric LiNbO_3 single crystals

This paper investigates the photovoltaic properties of miscut LiNbO3 single crystal with different thicknesses under irradiation of a 248 nm ultraviolet laser pulse with 20 ns duration without an applied bias. Nanosecond photovoltaic response is observed and faster rise time is obtained in thinner samples. In accord with the 248 nm laser duration, the full width at half maximum of the photovoltaic signals keeps a constant of ~ 20 ns. With decrease of the crystal thickness, the photovoltaic sensitivity was improved rapidly at first and then decreased, and the maximum photovoltage occurred at 0.38 mm-thick single crystal. The present results demonstrate that decreasing the LiNbO3 single crystal thickness can obtain faster response time and improve the photovoltaic sensitivity.

Holographic Storage Properties of In:Fe:Mn:LiNbO_3 Crystals

In：Fe：Mn：LiNbO3（LN） crystals were grown in air atmosphere by Czochralski method with different concentration of In （0, 1, 2, 3 mol%） in the melts, while the contents of Fe2O3 and MnO were 0.1 and 0.5 mol%, respectively. The location of doping ions was analyzed by Ultravioletvisible absorption spectra and differential thermal analysis. The diffraction efficiency （η）, writing time （τw） and erasure time （τe） of the crystals were measured by two-beam coupling experiment. The dynamic range and photorefractive sensitivity have also been calculated. The results showed that with the increase of In ions in the melt, the absorption edge of In：Fe：Mn：LN crystal shifts to the violet firstly and then makes the Einstein shift, the Curie temperature of crystal increases firstly and then decreases, the storage ratio speeds up, diffraction efficiency decreases, and dynamic range and photorefractive sensitivity increase. The mechanism of holographic storage properties of In：Fe： Mn：LN crystal with different doping concentration of In^3＋ was investigated, suggesting the In： Fe：Mn：LN crystals are excellent holographic storage materiel with better synthetical properties than Fe：Mn：LN crystals.

Study on the Growth and Photorefractive Properties of In:Fe:Cu:LiNbO_3 Crystals

Fe（0.2 mol%）：Cu（0.04 mol%）：LiNbO3 crystals with different doping concentration of In^3＋ （0, 1.0, 2.0, 3.0mol%） were grown by Czochralski method, and then oxidized and reduced. The infrared transmittance spectra of crystals were measured to investigate the location of doping ion and its threshold concentration. The photorefractive properties of the crystals were tested by two beam coupling experiment. The results showed that the threshold concentration of In ions is 2.0～ 3.0 mol% and In ions take the place of NbLi^4＋ to form （ InLi^2＋） before reaching its threshold concentration, and then the location of normal Nb ions. In the （2.0 mol%）：Fe：Cu：LiNbO3 crystal with the oxidation treatment having the highest diffraction efficiency （η = 45.8%）, the photo-damage resistance threshold value R of In（3.0 mol%）：Fe：Cu：LiNbO3 was 3.67×10^4 W/cm^2 which was two orders of magnitude higher than that of Fe：Cu：LiNbO3 crystal （4.30×10^2 W/cm^2）. And the photo-damage resistance ability was enhanced by oxidized treatment. The In（2.0～3.0 mol%）：Fe：Cu：LiNbO3 crystals with oxidized treatment have the best photorefractive properties.

Zn∶Mg∶LiNbO_3抗光折变性能机理的研究

LiNbO 3crystal possesses electro optic effect and nonlinear optical effect.Bec ars e it is easy to generate photo damage(photorefractive) for LiNbO 3.This limits i ts application in some fields.When doping 6mol% ZnO or 5mol% MgO in LiNbO 3 cry stal to grow Zn∶LiNbO 3 or Mg∶LiNbO 3 crystal,the photo damage resistance ab ility fo these two crystals is two orders of magnitude higher than that of LiNbO 3.We doped 3mol% ZnO and 3mol% MgO to grow Zn∶Mg∶LiNbO 3 crystal and used Fourier spectrophotometer to measure the infrared transmission spectra.The waven umber range to measure the OH - stretched vibration transmission spectra of Zn ∶LiNbO 3,Mg∶LiNbO 3 and Zn∶Mg∶LiNbO 3 crystal is 3200 4000cm -1 .The measurement result is that the OH - stretched vibration absorption peak of Zn( 6mol%):LiNbO 3,Mg(5mol%):LiNbO 3 and Zn(3mol%):Mg(3mol%):LiNbO 3 crystal is at 3535cm -1 (2.83μm),while that of pure LiNbO 3,Zn(3mol%):LiNbO 3 and M g(3mol%):LiNbO 3 is at 3484cm -1 (2.87μm).We take the direct obseration me thod of the focula distortion in crystal to measure the photorefractive threshol d value of these crystals and gained the result that the photorefractive thresho ld value of Zn(6mol%):LiNbO 3,Mg(5mol%):LiNbO 3 and Zn(3mol%):Mg(3mol%):LiNbO 3 increase above two orders of magnitude higher than pure LiNbO 3 crystal and the photorefractive threshold value of Zn(3mol%):LiNbO 3 and Mg(3mol%):LiNbO 3 is a little higher than that of pure LiNbO 3 crystal.The congruent compositio n ratio of LiNbO 3 is Li/Nb=0.946.A part of Nb 5+ take place Li + site to form the intrinsic defect antisite Nb 4+ Li .The charge transport proc ess in LiNbO 3 is due to this kind of intrinsic defect.Especially in high light intensity,the intrinsic defect is important.The quantity that make antisite Nb 4+ Li defect structure disappear when doping ions (Mg 2+ and Zn 2+ ) substitute for all Nb 4+ Li at Li + site is called the thre shold concentration for this impurity ion.At the same time the impurity ion star t to take place Nb site.The photo damage resistance impurity ion is to drive ant i site Nb Li from Li site to normal Nb site so that the OH - absorption peak shifts to 2.83μm from 2.87μm.The fact that the OH - absorption peak of Zn(3m ol%):Mg(3mol%):LiNbO 3 crystal shifts to 2.83μm from 2.87μm and its photo dam age resistance threshold value is two orders of magnitude higher than pure LiNbO 3 crystal shows that above analyse is reasonable.

掺杂LiNbO_3晶体生长及在体全息存储方面的应用研究

In this paper,the Fe:LiNbO 3,Ce:Fe:LiNbO 3 and Ce:Mn:LiNbO 3 crystals with n o defect,were grown from melt by Czochraski technique.The two doped LiNbO 3 cry stals were treated by heating reduction in Li 2O 3 powder,and Fe:LiNbO 3 crys tals were oxidized in air. The measurments on lattic constants and the absorption spectrum show that the doped crystals’ structure are regular and the optical pr operties are good.The absorption spectra,diffractive efficency,response time,sen sitivity,and photoconduction were measured.The properties of Ce:Fe:LiNbO 3 crys tals are η sat =0.25, Sη -1 =16.2mJ/mm 2, τ E/ τ W=6 .5, σ =2.99×10 -17 ;and the properties of Ce:Fe:LiNbO 3 crystals are η sat =0.70, Sη -1 =4.6mJ/mm 2, τ E/ τ W=7.2, σ =5. 42×10 -17 . The response speed of two doped LiNbO 3 crystals is faster than that of Fe:LiNbO 3 crystals.The diffractive efficiency was measured to be high er than 80% and with a broad angle range.Fe:LiNbO 3 crystals were oxidized in air in order to make the storage time longer and strength the diffractive effici ency.So it is a good kind of Volume Holographic memory materials.And it is shown in our experiment that Ce:Fe:LiNbO 3 crystals is more sensitive to 633nm than Fe:LiNbO 3 crystals,it is more fit for He Ne laser and is a better materials o f Volume Holographic Storge.

Zn∶In∶Fe∶LiNbO_3晶体的生长及其二波耦合效应的研究

ZnO(4mol%),In 2O 3(1mol%)and Fe 2O 3(0.05mol%)were doped in LiNbO 3 and Czochralski method was used to grow Zn∶In∶Fe∶LiNbO 3 crystal.The diameter of the crystal we grew is 30mm.The technology parameter we took is that the axial temperature gradient is 40℃/cm,the growth rate is 1mm/h, the rotation rate is 15-25r/min,the temperature of polarization is 1220℃ and the current density of polarization is 5mA/cm 2.The wafer dimension is 10mm×10mm×3mm and was covered in Li 2CO 3 powder to reduce.The reduction temperature is 500℃ and reduction time is 30 hours. OH - stretch vibration transmission spectra were measured by Fourier infrared spectrophotometer. There are two absorption peaks in OH - spectra of Zn∶In∶Fe∶LiNbO 3,in which one is at 3534cm -1 (2.83μm) and the other is at 3505cm -1 (2.85μm).The peak at 2.85μm is far lower than that at 2.83μm. Because of the threshold effect of Zn 2+ and In 3+ ,the peak at 2.83μm is generated and the peak at 2.85μm is related with Fe 3+ .In LiNbO 3 only doped with Fe,Li + site is taken place by Fe 3+ .When doping Zn 2+ and In 3+ in high concentration,these two ions take place Nb that is at Li site and Fe 3+ substitutes for Nb 5+ at the same time.The interaction between Fe 3+ and OH - make the OH - peak shift to 2.85μm.

OH^- absorption and nonvolatile holographic storage properties in Mg:Ru:Fe:LiNbO_3 crystal as a function of Mg concentration

Mg：Ru：Fe：LiN-bO3 crystals with various concentrations of MgO （in mole） and fixed content of RuO2 and Fe203 （in mass） are grown with the Czochralski method from the congruent melt. Their infrared transmission spectra are mea- sured and discussed to investigate the defect structure. With the increase of Mg2＋ concentration the blue nonvolatile holographic storage capability is enhanced. The nonvolatile holographic storage properties of dual-wavelength recording of Mg（7 mol%）：Ru：Fe：LiNbO3 nonvolatile diffraction efficiency, response time, and nonvolatile sensitivity reach 59.8%, 70 s, and 1.04 cm/J, respectively. Comparing Mg（7 mol%）：Ru：Fe：LiNbO3 with Ru：Fe：LiNbO3 crystal, the response time is shortened apparently. The nonvolatile diffraction efficiency and sensitivity are raised largely. The mechanism in blue photorefractive nonvolatile holographic storage is discussed.

掺杂的化学计量比LiNbO_3单晶物理化学性能的改进

Lithium niobate LiNbO 3 is one of the most widely used non linear crystals.The melt grown crystals show typical non stoichiometric character.In the congruent crystal there are 5% of anti site Nb 5+ which are compensated by Li + vacancies.This kind of defect structure limits application of the crystal in several cases.In the ordered stoichiometric structure there are merely about 0.01% of anti site Nb 5+ ions. Non doped stoichiometric crystals exhibit significant changes of physical properties as compared with congruent ones,i.e. the blue shift of the absorption edge the narrowing of the spectral lines in EPR and NMR,Raman OH vibration etc.

Investigation of Mechanism of Co-doped Zn^(2+) and In^(3+) Influence on Optical Properties of Fe∶LiNbO_3

Doping Zn with the concentration of 3mol% and In 2O 3 with different concentrations in Fe∶LiNbO 3, Zn∶In∶ Fe∶ LiNbO 3 crystals were grown. The infrared spectra of the crystals were measured and the mechanism of the OH-, absorption peak shifting was studied. The diffraction efficiency, response time and photoconduction of the crystals were measured. The mechanisms of the photoconduction increasing, diffraction efficiency decreasing and response time shorting for those crystals were studied.

Improvement in refractive-index change in LiNbO3：Ce：Cu by applying an external electric field

By jointly solving two-centre material equations with a nonzero external electric field and coupled-wave equations, we have numerically studied the dependence of the non-volatile holographic recording in LiNbO3：Ce：Cu crystals on the external electric field. The dominative photovoltaic effect of the non-volatile holographic recording in doubly doped LiNbO3 crystals is directly verified. And an external electric field that is applied in the positive direction along the c-axis （or a large one in the negative direction of the c-axis） in the recording phase and another one that is applied in the negative direction of the c-axis in the fixing phase are both proved to benefit strong photorefractive performances. Experimental verifications are given with a small electric field applied externally.

Effect of dopant concentration on the spectra characteristic in Zr^(4+) doped Yb:Nd:LiNbO_3 crystals

A series of Yb：Nd：LiNbO3 crystals tridoped with various concentrations of Zr4＋（1 mol.%, 2 mol.% and 4 mol.%） were grown by the Czochralski technique from the congruent melt. The X-ray powder diffraction, UV-Vis-NIR absorption spectra and IR transmittance spectra were measured to analyze the crystal composition and defect structure. The Zr4＋, Yb3＋ and Nd3＋ ions in LiNbO3 crystal had two effects： volume compensation effect and ion valence state compensation effect. The Zr O2 doping threshold concentration was nearly 2.0 mol.%. The fluorescence emissions of Nd3＋ ions and Yb3＋ ions were observed under 808 nm excitation. The intensity of fluorescence emissions enhanced with the increasing of the Zr4＋ doping concentrations. The Zr：Yb：Nd：LiNbO3 crystals with 4 mol.% doping concentration of Zr4＋ ion revealed strong emission around 1 μm, which is of great significance for laser materials.

The mechanism of the UV band edge photorefractivity suppression in highly doped LiNbO3：Zr crystals

The ultraviolet(UV) band edge photorefractivity of LiNbO_3:Zr at 325 nm has been investigated. The experimental results show that the resistance against photorefraction at 325 nm is quite obvious but not as strong as that at 351 nm, when the doping concentration of Zr reaches 2.0 mol%. It is reported that the photorefractivity in other tetravalently doped LiNbO_3 crystals, such as LiNbO_3:Hf and Li NbO_3:Sn, is enhanced dramatically with doping concentration over threshold. Here we give an explicit explanation on such seemly conflicting behaviors of tetravalently doped LiNbO_3, which is ascribed to the combined effect of increased photoconductivity and the absorption strength of the band edge photorefractive centers.

Experimental evidence of Bloch surface waves on photonic crystals with thin-film LiNbO_3 as a top layer

Strong nonlinear, electro-optical, and thermo-optical properties of lithium niobate(LN) have gained much attention. However, the implementation of LiNbO_3 in real devices is not a trivial task due to difficulties in manufacturing and handling thin-film LN. In this study, we investigate an optical device where the Bloch surface wave(BSW) propagates on the thin-film LN to unlock its properties. First, access to the LN film from air(or open space) is important to exploit its properties. Second, for sustaining the BSW, one-dimensional photonic crystal(1DPhC) is necessary to be fabricated under the thin-film LN. We consider two material platforms to realize such a device: bulk LN and commercial thin-film LN. Clear reflectance dips observed in far-field measurements demonstrate the propagation of BSWs on top of the LN surface of the designed 1DPhCs.

Tunable rectangular array illuminator in periodically poled LiNbO_3 crystal

An electro-optic tunable rectangular array illuminator in one-dimensional periodically poled LiNbO3 （PPLN） crystal is presented experimentally which result is in good agreement with results from simu- lation. The illuminator is formed based on the Talbot self-imaging effect by applying an electric field on PPLN. The intensi~.y distribution of rectangular array could be precisely modulated. Compared with other array illuminators, this tunable illuminator uses a lower voltage and could get a more concentrated intensity distribution. The influence of the incident angle to the self-imaging patterns is studied for the first time.