CN101323981A - Use of birefraction borate crystal - Google Patents

Use of birefraction borate crystal Download PDF

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CN101323981A
CN101323981A CNA2008100843882A CN200810084388A CN101323981A CN 101323981 A CN101323981 A CN 101323981A CN A2008100843882 A CNA2008100843882 A CN A2008100843882A CN 200810084388 A CN200810084388 A CN 200810084388A CN 101323981 A CN101323981 A CN 101323981A
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crystal
optical
birefringece
borate
birefringence
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CN101323981B (en
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陈小龙
何明
王皖燕
蔡格梅
许燕萍
刘军
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Abstract

The invention relates to an optical borate-series crystal with double refraction and application thereof. The borate-series crystal with double refraction has the chemical formula of ReBa3B9O18 (Re equals to Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu). The crystals are all uniaxial negative crystals, which have the birefringence of about 0.08 to 0.15 in the visible light band. The crystals in the series are easy to be incised, ground, polished and stored, are water immiscible, non-deliquescent and stable in air, and are suitable for being used for producing optical communication elements such as optoisolators, circulators, light beam shifters, optical polarizers and optical modulators, etc., in particular for producing polarizing prisms, phase delaying devices and electro-optical modulators with various purposes. The devices utilize the refraction index property of the optical borate-series crystal, particularly the larger birefringence (ne-no) thereof.

Description

A kind of purposes of birefraction borate crystal
Technical field
The present invention relates to double refraction optics field of crystals, particularly relate to a kind of borate-based ReBa 3B 9O 18The birefringece crystal of (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) and uses thereof.
Background technology
Birefringent phenomenon is one of key character of showing when propagating in photosensitiveness heterogeneous body crystal of light.When light is propagated in photosensitiveness heterogeneous body (as: crystal beyond the isometric system), except that indivedual special directions (along optical axis direction), can change its vibration characteristic, it is orthogonal to be decomposed into two electric vector direction of vibration, the velocity of propagation difference, the two bundle polarized light that specific refractory power does not wait, this phenomenon is called double refraction, and such crystal is called birefringece crystal.A branch of in the two-beam observes general the law of refraction, is called ordinary light (o light), its specific refractory power n oExpression, another bundle is not observed general the law of refraction, is called non-ordinary light (e light), its specific refractory power n eExpression.Utilize the characteristic of birefringece crystal can obtain line polarized light, realize the displacement of light beam etc.Thereby make birefringece crystal become the making optoisolator, circulator, pattern displacement device, sealed cell critical materials such as optical polariser and optical modulator.
Birefringent material commonly used mainly contains calcite, rutile, LiNbO 3, YVO 4And α-BaB 2O 4Crystal etc.Yet calcite crystal mainly exists with natural form, and synthetic is difficulty relatively, and stock size is all smaller, and foreign matter content can't satisfy the requirement of large size optics polarization element than higher, and is easy to cleavage, and processing is difficulty relatively, and the crystal utilization ratio is low.Rutile also mainly exists with natural form, and synthetic is difficulty relatively, and size is less, and hardness is big, is difficult to processing.LiNbO 3Crystal is easy to obtain large-size crystals, but degree of birefringence is too little.YVO 4Be a kind of well behaved synthetic birefringence crystal, but because YVO 4The fusing point height must use iridium crucible to carry out crystal growth, and growth atmosphere is weak oxygen atmosphere, thereby has the problem of appraising at the current rate of v element when growth, and makes crystal mass descend, and also is difficult for obtaining high-quality crystal.α-BaB 2O 4Owing to have solid-state phase changes, be easy in crystal growing process, ftracture.Given this, be necessary very much to seek a kind of growth that is easy to, stable in properties and birefringece crystal with big degree of birefringence.The borate compound that Inst. of Physics, CAS's crystal growth group was reported a series of isomorphisms in 2004 is consulted document 1:Li, X.Z.; Wang, C.; Chen, X.L.; Li, H.; Jia, L.S.; Wu, L.; Du Y.X.; Xu, Y.P.Inorg.Chem.2004,43,8555.The chemical formula of this series compound is ReBa 3B 9O 18(Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu).Their spacer all is P6 3/ m, basic structural unit are the B that is arranged in parallel along the c axle 3O 6The plane group, this plane group might cause big degree of birefringence.But accurately measure the crystalline specific refractory power and need larger-size, optical quality monocrystalline preferably.And above-mentioned document has just synthesized powdered sample, does not obtain valuable crystal prototype.Therefore, at present, obtain the borate-based ReBa of monocrystalline 3B 9O 18It is the technical problem that needs to be resolved hurrily that the birefringece crystal of (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) comes its degree of birefringence measurement.
Summary of the invention
In order to overcome above-mentioned technical problem, one of purpose of the present invention provides a kind of ReBa 3B 9O 18The double refraction borate crystal that (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) is borate-based.
Another object of the present invention provides a kind of above-mentioned crystalline purposes.
To achieve these goals, the present invention has adopted following technical scheme:
The invention provides a kind of ReBa 3B 9O 18(Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) borate-based birefringece crystal, preferred monocrystalline, wherein, this crystal is transparent and be uniaxial negative crystal n e＜n oCrystalline degree of birefringence (n e-n o) numerical values recited is about 0.08-0.15; This crystal is easy to processing and preserves, and water insoluble, and deliquescence is not stable in the air, is applicable to making.
Wherein, preferred ReBa 3B 9O 18(Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) borate-based birefringece crystal size is not less than 1 * 1 * 0.5mm 3, more preferably 6 * 6 * 3～12 * 12 * 7mm 3
The invention provides a kind of ReBa 3B 9O 18The purposes of the birefringece crystal that (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) is borate-based, described borate-based birefringece crystal can be used for making light communication element, for example optoisolator, circulator, pattern displacement device, optical polariser and optical modulator etc.Especially for making ahrens prism, phase delay device and electro-optical modulation device etc.These devices use be the crystalline refractive index characteristic, particularly bigger degree of birefringence (n e-n o), this crystal is 0.10-0.12 in the degree of birefringence size of visible light wave range.
ReBa of the present invention 3B 9O 18(Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) borate-based birefringece crystal, can carry out single crystal growing with the high-temperature fusant method, and have following character: crystal is transparent; Crystal is uniaxial negative crystal n e＜n oCrystalline degree of birefringence (n e-n o) numerical values recited is about 0.08-0.15.This crystal is easy to cutting, grinds, polishes and preserves simultaneously, and water insoluble, deliquescence is not stable in the air, so be very suitable for making above-mentioned optics.
Description of drawings
Accompanying drawing 1 is ErBa 3B 9O 18The crystalline prism;
Accompanying drawing 2 is YBa 3B 9O 18The crystalline prism;
Accompanying drawing 3 is ErBa under the different wave length 3B 9O 18The crystalline specific refractory power;
Accompanying drawing 4 is ErBa 3B 9O 18The value of each coefficient in the crystalline dispersion equation;
Accompanying drawing 5 is YBa under the different wave length 3B 9O 18The crystalline specific refractory power;
Accompanying drawing 6 is YBa 3B 9O 18The value of each coefficient in the crystalline dispersion equation;
Accompanying drawing 7 is a birefringent wedge crystal polarization beam apparatus synoptic diagram;
Accompanying drawing 8 is the optoisolator synoptic diagram;
Accompanying drawing 9 is pattern displacement device synoptic diagram.
Embodiment
At first, ReBa 3B 9O 18The growth of the double refraction monocrystalline that (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) is borate-based adopts melting method to carry out, and this sentences the YBa that grows 3B 9O 18And ErBa 3B 9O 18Two kinds of crystal are that example is explained, and its concrete growth method can be consulted Chinese patent " a kind of preparation method of scintillation crystal barium yttrium borate and the purposes " (application number: 200710063683.5) in having applied for.By the method for this patent, can prepare the ReBa of different rare earth elements 3B 9O 18The double refraction monocrystalline that (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) is borate-based, just growth temperature changes to some extent with the change of element, repeats no more the concrete process of growth of different elements here.Such as, ErBa 3B 9O 18Crystalline growth method and YBa 3B 9O 18Crystal is basic identical, and that different is ErBa 3B 9O 18Fusing point be 1039 ℃, other growth parameter(s) then with YBa 3B 9O 18Crystal is similar.Specific refractory power to monocrystalline has adopted prism method to measure, and its basic skills is consulted State Standard of the People's Republic of China's " test method of crystal refractive index " (GB/T 16863-1997).Wherein, respectively with refraction index test sample ErBa 3B 9O 18Crystal and YBa 3B 9O 18Crystal is made prism as depicted in figs. 1 and 2, because crystal is thinner, they lump together with one or two glass cements respectively and grind and polishing.Prismatical rib is parallel to crystalline optical axis [001] direction.Fig. 1 is ErBa 3B 9O 18The crystalline prism, utilizing goniometer to measure the crystalline prism angle is 30 ° 10 ' 25 ".Fig. 2 is YBa 3B 9O 18The crystalline prism, utilizing goniometer to measure the crystalline prism angle is 17 ° 20 ' 44 ".Wherein end face ABC is perpendicular to the direction of optical axis, and prismatical two logical light faces are respectively perpendicular to end face and all optical grade polishings.Face AA ' B ' B is the plane of incidence of light, and face AA ' C ' C is an exit facet.YBa 3B 9O 18And ErBa 3B 9O 18Equally all be uniaxial negative crystal, their specific refractory poweres under same incident wavelength are very close, as:
Figure A20081008438800061
During incident wavelength, ErBa 3B 9O 18E light and the specific refractory power of o light be respectively: 1.6059 and 1.7327, and YBa 3B 9O 18The value of crystal correspondence is 1.6014 and 1.7224, and the difference of these two kinds of crystalline specific refractory poweres is very little as can be seen, and degree of birefringence is also very close, all at 0.10-0.12.Because the B in this specific character of specific refractory power and the crystal 3O 6Anionic group is relevant, and is very little with its rare earth ion relation, can reason out the series compound ReBa of this isomorphism thus 3B 9O 18Other compound also should be the uniaxial negative crystal with big degree of birefringence in (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu).
Embodiment 1ErBa 3B 9O 18The crystal refractive index test
Fig. 3 has listed the refraction index test result from purple light to 8 different wave lengths of red visible scope.Test result shows, ErBa 3B 9O 18Crystal is negative single shaft crystalline substance, and its degree of birefringence is about-0.11 in visible wavelength range.(404.7nm) specific refractory power of purple light ordinary light is 1.7327, and (656.3nm) specific refractory power of ruddiness ordinary light is 1.7059, its chromatic dispersion n Purple-n Red=0.0268.
ErBa 3B 9O 18Crystalline specific refractory power-dispersion equation can be expressed by the Sellmeier equation of four parameters:
Figure A20081008438800062
λ represents the vacuum medium wavelength in the formula N is a specific refractory power, and each coefficient fitting result is as shown in Figure 4 in the following formula when 295K.Utilize this equation in certain wavelength region, to calculate refractive index value.
Embodiment 2YBa 3B 9O 18The crystal refractive index test
Fig. 5 has listed the refraction index test result from purple light to 8 different wave lengths of red visible scope.Test result shows, YBa 3B 9O 18Crystal is negative single shaft crystalline substance, and its degree of birefringence is about-0.12 in visible wavelength range.(404.7nm) specific refractory power of purple light ordinary light is 1.7291, and (656.3nm) specific refractory power of ruddiness ordinary light is 1.7000, its chromatic dispersion n Purple-n Red=0.0291.
YBa 3B 9O 18Crystalline specific refractory power-dispersion equation: the Sellmeier equation of four parameters
Figure A20081008438800071
λ represents the vacuum medium wavelength in the formula
Figure A20081008438800072
N is a specific refractory power, and each coefficient fitting result is as shown in Figure 6 in the following formula when 295K.Utilize this equation in certain wavelength region, to calculate refractive index value.
Embodiment 3NdBa 3B 9O 18The calculating of crystal refractive index
These a series of boratory big specific refractory poweres come from its group B 3O 6Optical anisotropy.B 3O 6By 3 BO 3Group constitutes, and BO 3Group is parallel to the plane with very different perpendicular to the planar polarization under the effect of electric field outside.And according to the Wooster rule, the crystal of all laminate structures if do not contain the OH group, all is negative optical axis crystal, consults document [Wooster, W.A.1931, Zeit.Krist., 80,495-503].Utilize the Theoretical Calculation of Bragg, consult [Ye Danian, structure optical mineralogy, Geology Publishing House, 1998] and can calculate NdBa about specific refractory power 3B 9O 18Crystal refractive index, n eIn the 1.58-1.62 scope, n oIn the 1.70-1.73 scope, be still uniaxial negative crystal, degree of birefringence is in the 0.1-0.13 scope.
Embodiment 4TbBa 3B 9O 18The calculating of crystal refractive index
These a series of boratory big specific refractory poweres come from its group B 3O 6Optical anisotropy.B 3O 6By 3 BO 3Group constitutes, and BO 3Group is parallel to the plane with very different perpendicular to the planar polarization under the effect of electric field outside, is similar to CO 3Group.Utilize the Theoretical Calculation of Bragg, consult [Ye Danian, structure optical mineralogy, Geology Publishing House, 1998] and can calculate TbBa about specific refractory power 3B 9O 18Crystal refractive index, n eIn the 1.57-1.62 scope, n oIn the 1.69-1.73 scope, be still uniaxial negative crystal, the degree of birefringence numerical values recited is the 0.1-0.14 scope.
Application Example 1
Birefringent wedge crystal polarization beam apparatus, as shown in Figure 7, the birefringece crystal of a wedge type, the orientation of optical axis is as shown in Figure 7.Can be divided into two bunch polarized light through crystal after a branch of natural light incident.Degree of birefringence is big more, and two-beam can separate far more, is convenient to the separation of light beam.
Application Example 2
Optoisolator, faraday's optical rotator that incoming beam polarization plane rotation 45 is spent can be placed one a pair of 45 degree that are each other to intersect between the birefringece crystal polarizer of placing, then can constitute an optoisolator, it only allows the light beam of forward-propagating by this system, and the light beam of backpropagation is blocked.Fig. 8 a represents that the incident light beam can pass through, and Fig. 8 b represents that reflected light has been prevented from.
Application Example 3
The pattern displacement device is processed a birefringece crystal, makes its axial plane and rib θ at angle, shown in Fig. 9 a.After the natural light vertical incidence, can be divided into the mutually perpendicular line polarized light of two bundle direction of vibration, shown in Fig. 9 b, be respectively o light and e light.Degree of birefringence is big more, and two-beam can separate far more, is convenient to the separation of light beam.
It should be noted that herein only with ErBa 3B 9O 18, YBa 3B 9O 18, NdBa 3B 9O 18, TbBa 3B 9O 18Crystal is that example is to ReBa provided by the present invention 3B 9O 18(Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) borate-based birefringece crystal is illustrated, but to what those skilled in the art may be obvious that is, because the B in specific refractory power compromise characteristic and the crystal 3O 6Anionic group is relevant, and is very little with its rare earth ion relation, therefore the ReBa that can summarize this isomorphism 3B 9O 18Other crystal during (Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu) is borate-based also should be the uniaxial negative crystal with big degree of birefringence.Equally, on the technical solution of the present invention basis, also can carry out variations and modifications, but not break away from the generalized scope of the present invention's claims required for protection technical scheme of the present invention.

Claims (8)

1, a kind of borate-based birefringece crystal, the chemical formula of these a series of birefringece crystals is ReBa 3B 9O 18(Re=Y, Pr, Nd, Sm, Eu, Gd, Tb, Er, Dy, Ho, Tm, Yb and/or Lu), wherein, described crystal is transparent and be uniaxial negative crystal n e＜n o
2, birefringece crystal as claimed in claim 1 is characterized in that, described crystalline degree of birefringence (n e-n o) numerical values recited be 0.08 to 0.15.
3, birefringece crystal as claimed in claim 1 is characterized in that, described crystal is easy to processing and preserves, and water insoluble, and deliquescence is not stable in the air, and these character satisfy the basic demand that double refraction is used.
As each described birefringece crystal of claim 1-3, it is characterized in that 4, described crystal is a monocrystalline.
5, birefringece crystal as claimed in claim 4 is characterized in that, described crystalline size is not less than 1 * 1 * 0.5mm 3
6, a kind ofly want the purposes of each described birefringece crystal of 1-5 as right, described crystal is used to make light communication element, and this crystal is 0.08-0.15 in the degree of birefringence numerical values recited of visible light wave range.
7, purposes as claimed in claim 6 is characterized in that, described crystal is used for optoisolator, circulator, pattern displacement device, optical polariser or optical modulator.
8, purposes as claimed in claim 6 is characterized in that, described crystal is used to make ahrens prism, phase delay device or electro-optical modulation device.
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