WO2024036655A1 - 硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法 - Google Patents

硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法 Download PDF

Info

Publication number
WO2024036655A1
WO2024036655A1 PCT/CN2022/114468 CN2022114468W WO2024036655A1 WO 2024036655 A1 WO2024036655 A1 WO 2024036655A1 CN 2022114468 W CN2022114468 W CN 2022114468W WO 2024036655 A1 WO2024036655 A1 WO 2024036655A1
Authority
WO
WIPO (PCT)
Prior art keywords
crystal
gallium
solid solution
lanthanum
crystals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/114468
Other languages
English (en)
French (fr)
Inventor
于浩海
路大治
王玉周
张怀金
王继扬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to US17/953,362 priority Critical patent/US12436316B2/en
Publication of WO2024036655A1 publication Critical patent/WO2024036655A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C01G33/006—Compounds containing niobium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/353—Frequency conversion, i.e. wherein a light beam is generated with frequency components different from those of the incident light beams
    • G02F1/3544—Particular phase matching techniques

Definitions

  • the invention relates to the technical fields of nonlinear optical crystals and lasers, and more specifically to an effective nonlinear optical coefficient optimization method for gallium lanthanum silicate solid solution crystals.
  • the lanthanum gallium silicate family crystal (the general structural formula is A 3 BC 3 D 2 O 14 and contains four polyhedral groups AO 8 , BO 6 , CO 4 and DO 4 ) mainly includes lanthanum gallium niobate (LGN) crystal, tantalum Lanthanum gallium oxide (LGT) crystal and lanthanum gallium silicate (LGS) crystal, etc.
  • LGN lanthanum gallium niobate
  • LGT Lanthanum gallium oxide
  • LGS lanthanum gallium silicate
  • Effective mid-frequency infrared laser output In the process of nonlinear frequency conversion, the effective nonlinear coefficient of the nonlinear crystal material determines its conversion efficiency. The size of the effective nonlinear coefficient depends on the nonlinear coefficient of the material and the refractive index dispersion equation. The existing gallium lanthanum silicate family The phase matching condition of the crystal determines that the effective nonlinear coefficient of infrared frequency conversion in this type of crystal is small, which limits its frequency conversion efficiency.
  • gallium lanthanum silicate family solid solution crystals improving the effective nonlinear optical coefficients while maintaining the excellent properties of this family of crystals is an urgent problem that those skilled in the art need to solve.
  • the present invention provides an effective nonlinear optical coefficient optimization method for gallium lanthanum silicate solid solution crystals; the solid solution crystal is formed by adjusting the component ratio of gallium lanthanum silicate crystals with the same structure, and the B-position group is and D-site groups are mixed with different ions to regulate the polyhedral lattice structure and degree of distortion of the crystal, as well as adjust the refractive index and refractive index dispersion of the solid solution crystal, thereby reducing the phase matching angle and improving the nonlinear optical coefficient.
  • Optimize effective nonlinear optical coefficients Optimize effective nonlinear optical coefficients.
  • gallium lanthanum silicate crystal A 3 BC 3 D 2 O 14 mainly includes lanthanum gallium niobate (LGN) crystal, gallium tantalate Lanthanum (LGT) crystals, lanthanum gallium silicate (LGS) crystals, etc., form solid solution crystals by adjusting the proportion of gallium lanthanum silicate crystals with the same structure, allowing different ions to mix in the polyhedral groups, changing the solid solution crystal The polyhedral lattice structure, distortion degree, refractive index and refractive index dispersion.
  • LGN lanthanum gallium niobate
  • LGT gallium tantalate Lanthanum
  • LGS lanthanum gallium silicate
  • solid solution crystals are formed by dissolving lanthanum gallium niobate crystals, lanthanum gallium tantalate crystals or lanthanum gallium silicate crystals with the same crystal structure and similar components in different proportions, so that the B position of the lanthanum gallium silicate group crystal is and/or D bit structure changes.
  • the B-position group adopts Ga 3+ , Nb 5+ , Ta 5+ , Ti 4+ , Zr 4+ , Hf 4+ , Sn 4+ , Sb 5+ plasma mixed occupation, to control the refractive index, and adjust the refractive index of different ions.
  • Different electron cloud structures regulate the refractive index and refractive index dispersion, thereby reducing the phase matching angle and increasing the effective nonlinear optical coefficient.
  • the lanthanum gallium niobate (LGN) crystal and the gallium gallium tantalate (LGN) crystal with the same crystal structure and similar composition are LGT) crystals dissolve in each other in different proportions to form lanthanum gallium niobate tantalate (LGNT) solid solution crystal;
  • the B-site group adopts three types: gallium ion (Ga 3+ ), niobium ion (Nb 5+ ) and tantalum ion (Ta 5+ )
  • the seed ions are shared to control the distortion of the B-site polyhedral group.
  • the crystal is a gallium gallium niobate tantalate (LGNT) solid solution crystal.
  • the component ratio of the gallium lanthanum silicate family crystal is 0.9:0.1 or 0.7:0.3. Specifically, The molar ratio of the four raw materials of La 2 O 3 , Ga 2 O 3 , Nb 2 O 5 , and Ta 2 O 5 is 0.3:0.55:0.045:0.005 or 0.3:0.55:0.035:0.015; this series of solid solution crystals maintains niobium
  • the crystal structure of lanthanum gallium oxide (LGN) and lanthanum gallium tantalate (LGT) can continuously adjust the refractive index of this family of crystals, thereby changing the phase matching angle and increasing the effective nonlinear optical coefficient.
  • the D-site group is mixed with Ga 3+ , Ge 4+ , and Si 4+ plasma to control the size of the D-site polyhedral distortion.
  • the electron cloud structures of different ions are different, which can control the refractive index and refractive index dispersion, thereby reducing The phase matching angle increases the effective nonlinear optical coefficient.
  • different ions are mixed in the two types of polyhedral groups at the B position and the D position.
  • Ga 3+ and Zr 4+ ions are mixed at the B position, and Ga 3+ and Si 4+ ions are mixed at the D position. occupies, and then forms a gallium zirconate lanthanum silicate solid solution crystal, simultaneously controls the B-site and D-site polyhedral distortion, increases the nonlinear optical coefficient, and simultaneously controls the crystal refractive index and refractive index dispersion, thereby reducing the phase matching angle and increasing the effective nonlinearity.
  • Optical coefficient is preferably, Optical coefficient.
  • the present invention provides an effective nonlinear optical coefficient optimization method for gallium lanthanum silicate solid solution crystals; by adjusting the components of the gallium lanthanum silicate crystals with the same structure A solid solution crystal is formed proportionally, and different ions are used to mix the B-site group and the D-site group to regulate the polyhedral lattice structure and degree of distortion of the crystal, as well as adjust the refractive index and refractive index dispersion of the solid solution crystal to achieve phase matching angles.
  • the reduction and the improvement of nonlinear optical coefficients ultimately optimize the effective nonlinear optical coefficients.
  • Figure 1 is a diagram showing the lanthanum gallium niobate (LGNT) solid solution crystal, lanthanum gallium niobate (LGN) crystal and tantalum provided in Embodiment 2 of the present invention with Nb 5+ /Ta 5+ ratios of 0.9:0.1 and 0.7:0.3. Comparison of refractive index of lanthanum gallium oxide (LGT) crystal.
  • LGNT lanthanum gallium niobate
  • LGN lanthanum gallium niobate
  • LGT refractive index of lanthanum gallium oxide
  • Figure 2 is a diagram showing a comparison of the nonlinear optical coefficients of lanthanum gallium niobate tantalate (LGNT) solid solution crystals with Nb 5+ /Ta 5+ ratios of 0.9:0.1 and 0.7:0.3 provided in Embodiment 2 of the present invention.
  • LGNT lanthanum gallium niobate tantalate
  • Figure 3 is a diagram showing the lanthanum gallium niobate (LGNT) solid solution crystal, lanthanum gallium niobate (LGN) crystal and tantalum provided in Embodiment 2 of the present invention with Nb 5+ /Ta 5+ ratios of 0.9:0.1 and 0.7:0.3. Comparison of type I phase matching tuning curves of lanthanum gallium oxide (LGT) crystal.
  • LGNT lanthanum gallium niobate
  • LGN lanthanum gallium niobate
  • LGT lanthanum gallium oxide
  • Figure 4 is a diagram showing the lanthanum gallium niobate (LGNT) solid solution crystal, lanthanum gallium niobate (LGN) crystal and tantalum provided in Embodiment 2 of the present invention with Nb 5+ /Ta 5+ ratios of 0.9:0.1 and 0.7:0.3. Comparison of type II phase matching tuning curves of lanthanum gallium oxide (LGT) crystal.
  • LGNT lanthanum gallium niobate
  • LGN lanthanum gallium niobate
  • LGT lanthanum gallium oxide
  • Figure 5 is a schematic structural diagram of the gallium lanthanum silicate crystal A 3 BC 3 D 2 O 14 provided by the present invention.
  • the embodiment of the present invention discloses an effective nonlinear optical coefficient optimization method of the gallium lanthanum silicate family solid solution crystal, which is characterized in that the gallium lanthanum silicate family crystal A 3 BC 3 D 2 O 14 mainly includes lanthanum gallium niobate (LGN ) crystal, lanthanum gallium tantalate (LGT) crystal, lanthanum gallium silicate (LGS) crystal, etc., solid solution crystals are formed by adjusting the proportion of gallium lanthanum silicate family crystal components with the same structure, so that different ions can be carried out in polyhedral groups. Mixing changes the polyhedral lattice structure, distortion degree, refractive index and refractive dispersion of solid solution crystals.
  • LGN lanthanum gallium niobate
  • LGT lanthanum gallium tantalate
  • LGS lanthanum gallium silicate
  • lanthanum gallium niobate crystals, gallium lanthanum tantalate crystals or gallium lanthanum silicate crystals with the same crystal structure and similar components are dissolved in each other in different proportions to form solid solution crystals, making the gallium lanthanum silicate family
  • the B-site and/or D-site structure of the crystal changes.
  • the B-site group is mixed with Ga 3+ , Nb 5+ , Ta 5+ , Ti 4+ , Zr 4+ , Hf 4+ , Sn 4+ , and Sb 5+ plasma.
  • the D-position group is mixed with Ga 3+ , Ge 4+ , and Si 4+ plasma.
  • different ions are mixed in the two types of polyhedral groups at the B position and D position.
  • Ga 3+ and Zr 4+ ions are used at the B position, and Ga 3+ and Si are used at the D position. 4+ ions are mixed to form a solid solution crystal of gallium zirconate silicate.
  • the nonlinear optical crystal is a gallium gallium niobate solid solution crystal of the gallium silicate family. Its chemical formula is La 3 Ga 5.5 (Nb 1-x Ta x ) 0.5 O 14 . It belongs to the trigonal crystal system and has a 32-point group. Type I (the two incident light beams have the same polarization mode, both are e-light) and Type II phase matching (the two incident light beams have inconsistent polarization directions, one is o-light and the other is e-light), the corresponding effective two The first-order nonlinear coefficient is (a kind of bit match) and (Type II phase matching), ⁇ is the phase matching angle, is the azimuth angle.
  • the B-site group accommodates Ga 3+ , Nb 5+ , Ta 5+ , Ti 4+ , Zr 4+ , Hf 4+ , Sn 4+ , Sb 5+ and other ions, using different ion mixing methods. It can increase the distortion of the B-site group and increase the nonlinear optical coefficient; at the same time, there are certain differences in the electron cloud structures of different ions, which can adjust the refractive index and refractive index dispersion of the crystal, reduce the phase matching angle, and then increase Effective nonlinear optical coefficients.
  • Ga 3+ , Nb 5+ , Ta 5+ , Ti 4+ , Zr 4+ , Hf 4+ , Sn 4+ , Sb 5+ and other ions have similar ionic radii and have good lattice matching. Infinite solid solution crystals can be formed, and large-sized single crystals with high optical quality can be easily obtained.
  • the D-position group can also accommodate a variety of ions, such as Ga 3+ , Ge 4+ , and Si 4+ .
  • Example 1 Taking the lanthanum gallium niobate (LGNT) solid solution crystal that can be formed by lanthanum gallium niobate (LGN) crystal and lanthanum gallium tantalate (LGT) crystal as an example, we designed the Nb 5+ /Ta 5+ ratio It is a 0.5:0.5 lanthanum gallium niobate (LGNT) solid solution crystal. Its specific molar ratio of the four raw materials: La 2 O 3 , Ga 2 O 3 , Nb 2 O 5 , and Ta 2 O 5 is 0.3:0.55:0.025. :0.025. This crystal belongs to the trigonal crystal system and 32-point group.
  • LGNT lanthanum gallium niobate
  • the distortion of the B-site group increases, which is beneficial to increasing the nonlinear optical coefficient; at the same time, the crystal refractive index
  • the size of the refractive index dispersion changes accordingly, which can reduce the phase matching angle and help increase the effective nonlinear optical coefficient of the crystal.
  • Example 2 We design the following lanthanum gallium niobate (LGNT) solid solution crystals with different Nb 5+ /Ta 5+ ratios, such as Nb 5+ /Ta 5+ ratios of 0.9:0.1, 0.7:0.3, 0.3:0.7 , lanthanum gallium niobate (LGNT) solid solution crystals with different Nb 5+ /Ta 5+ ratios such as 0.1:0.9, including four specific types: La 2 O 3 , Ga 2 O 3 , Nb 2 O 5 , and Ta 2 O 5
  • the molar ratio of raw materials can be 0.3:0.55:0.045:0.005, 0.3:0.55:0.035:0.015, 0.3:0.55:0.015:0.035, 0.3:0.55:0.005:0.045.
  • This series of solid solution crystals also maintains the crystal structure of lanthanum gallium niobate (LGN) and lanthanum gallium tantalate (LGT). It can continuously adjust the refractive index of this family of crystals, thereby changing the phase matching angle and increasing the effective nonlinear optical coefficient. .
  • Example 3 Taking the solid solution crystal of lanthanum gallium zirconate (LGZr) and lanthanum gallium silicate (LGS) as an example, we can design the Zr 4+ /Si 4+ ratio to be 0.5 :0.5 La 3 Zr 0.5 Ga 5 Si 0.5 O 14 crystal, the specific molar ratio of the four raw materials La 2 O 3 , Ga 2 O 3 , ZrO 2 , and SiO 2 is 0.3:0.5:0.1:0.1.
  • the crystal belongs to the trigonal crystal system and 32-point group.
  • the B-site and D-site are respectively occupied by two ions: Ga 3+ /Zr 4+ and Ga 3+ /Si 4+ .
  • the distortion of the B-site group and the D-site group The increase in degree is conducive to increasing the nonlinear optical coefficient; at the same time, the refractive index and refractive index dispersion of the crystal change accordingly, which can reduce the phase matching angle and is conducive to increasing the effective nonlinear optical coefficient of the crystal.
  • Example 4 Taking the lanthanum gallium zirconate silicate (LZGS) solid solution crystal that can be formed by lanthanum gallium zirconate (LGZr) and lanthanum gallium silicate (LGS) as an example, we can design different Zr 4+ /Si 4+ ratios.
  • LZGS lanthanum gallium zirconate silicate
  • LZGS Lanthanum gallium zirconate silicate
  • solid solution crystals such as solid solution crystals with Zr 4+ /Si 4+ ratios of 0.9:0.1, 0.7:0.3, 0.3:0.7, 0.1:0.9, etc., among which La 2 O 3 , Ga
  • the molar ratio of the four raw materials 2 O 3 , ZrO 2 , and SiO 2 can be 0.3:0.5:0.18:0.02, 0.3:0.5:0.14:0.06, 0.3:0.5:0.06:0.14, 0.3:0.5:0.02:0.18.
  • This series of crystals also belongs to the trigonal crystal system and 32-point group.
  • the B-site and D-site are respectively occupied by two ions: Ga 3+ /Zr 4+ and Ga 3+ /Si 4+ , so that the B-site group and the D-site group Increasing the distortion of the group is conducive to increasing the nonlinear optical coefficient; simultaneously adjusting the refractive index and refractive index dispersion of the crystal can reduce the phase matching angle, which is conducive to increasing the effective nonlinear optical coefficient of the crystal.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，硅酸镓镧族晶体A 3BC 3D 2O 14主要包括铌酸镓镧LGN晶体、钽酸镓镧LGT晶体、硅酸镓镧LGS晶体等，通过调节同结构的硅酸镓镧族晶体组分比例形成固溶体晶体，使得不同的离子在多面体基团中进行混占，改变固溶体晶体的多面体格位结构、畸变程度、折射率和折射色散，实现相位匹配角度的降低和非线性光学系数的提高，最终优化有效非线性光学系数。

Description

硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法 技术领域
本发明涉及非线性光学晶体和激光技术领域，更具体的说是涉及一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法。
背景技术
硅酸镓镧族晶体(结构通式为A 3BC 3D 2O 14，包含AO 8、BO 6、CO 4和DO 4四种多面体基团)主要包括铌酸镓镧(LGN)晶体、钽酸镓镧(LGT)晶体和硅酸镓镧(LGS)晶体等。前期研究表明该族晶体中铌酸镓镧(LGN)晶体兼具宽透过范围和高激光损伤阈值的特点，是综合性能优秀的中红外非线性光学材料，已实现飞秒及纳秒的差频中红外激光有效输出。在非线性频率变换过程中，非线性晶体材料的有效非线性系数决定了其转换效率，有效非线性系数的大小依赖于材料的非线性系数和折射率色散方程，现有的硅酸镓镧族晶体的相位匹配条件决定了该类晶体中红外频率变换的有效非线性系数较小，限制了其频率变换效率。
因此，基于硅酸镓镧族固溶体晶体，在保持该族晶体优秀性能的基础上提升有效非线性光学系数是本领域技术人员亟需解决的问题。
发明内容
有鉴于此，本发明提供了一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法；通过调节同结构的硅酸镓镧族晶体组分比例形成固溶体晶体，并在B位基团和D位基团采用不同离子进行混占，调控晶体的多面体格位结构和畸变程度，以及调节固溶体晶体的折射率和折射率色散，实现相位匹配角度的降低和非线性光学系数的提高，最终优化有效非线性光学系数。
为了实现上述目的，本发明采用如下技术方案：
一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，其特征在于，硅酸镓镧族晶体A 3BC 3D 2O 14主要包括铌酸镓镧(LGN)晶体、钽酸镓镧(LGT)晶体、硅酸镓镧(LGS)晶体等，通过调节同结构的硅酸镓镧族晶体组分比例形成固溶体晶体，使得不同的离子在多面体基团中进行混占，改变固溶体晶体的多面体格位结构、畸变程度、折射率和折射率色散。
优选的，通过将晶体结构相同、组分相近的铌酸镓镧晶体、钽酸镓镧晶体或硅酸镓镧晶体按不同比例进行互溶，形成固溶体晶体，使得硅酸镓镧族晶体的B位和/或D位结构改变。
优选的，B位基团采取Ga 3+、Nb 5+、Ta 5+、Ti 4+、Zr 4+、Hf 4+、Sn 4+、Sb 5+等离子混占，调控折射率，不同离子的电子云结构不同，调控折射率和折射率色散，进而降低相位匹配角度，增大有效非线性光学系数，将晶体结构相同、组分相近的铌酸镓镧(LGN)晶体和钽酸镓镧(LGT)晶体按不同比例进行互溶，形成钽铌酸镓镧(LGNT)固溶体晶体；B位基团采取镓离子(Ga 3+)、铌离子(Nb 5+)和钽离子(Ta 5+)三种离子共占，调控B位多面体基团畸变大小，具体的，晶体为钽铌酸镓镧(LGNT)固溶体晶体，硅酸镓镧族晶体组分 比例为0.9:0.1或0.7:0.3，其具体的La 2O 3，Ga 2O 3，Nb 2O 5，Ta 2O 5四种原料的摩尔比为0.3:0.55:0.045:0.005或0.3:0.55:0.035:0.015；该系列固溶体晶体保持了铌酸镓镧(LGN)和钽酸镓镧(LGT)的晶体结构，可以连续地调节该族晶体的折射率，进而改变相位匹配角度，增大有效非线性光学系数。
优选的，D位基团采取Ga 3+、Ge 4+、Si 4+等离子混占，调控D位多面体畸变大小，同时不同离子的电子云结构不同，可以调控折射率和折射率色散，进而降低相位匹配角度，增大有效非线性光学系数。
优选的，同时在B位和D位两类多面体基团中采取不同离子进行混占，在B位采取Ga 3+、Zr 4+离子混占，D位采取Ga 3+、Si 4+离子混占，进而形成锆硅酸镓镧固溶体晶体，同时调控B位和D位多面体畸变，增大非线性光学系数，同时调控晶体折射率和折射率色散，进而降低相位匹配角度，增大有效非线性光学系数。
经由上述的技术方案可知，与现有技术相比，本发明公开提供了一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法；通过调节同结构的硅酸镓镧族晶体组分比例形成固溶体晶体，并在B位基团和D位基团采用不同离子进行混占，调控晶体的多面体格位结构和畸变程度，以及调节固溶体晶体的折射率和折射率色散，实现相位匹配角度的降低和非线性光学系数的提高，最终优化有效非线性光学系数。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1附图为本发明实施例2提供的Nb 5+/Ta 5+比例为0.9:0.1，0.7:0.3的钽铌酸镓镧(LGNT)固溶体晶体与铌酸镓镧(LGN)晶体和钽酸镓镧(LGT)晶体的折射率对比。
图2附图为本发明实施例2提供的Nb 5+/Ta 5+比例为0.9:0.1，0.7:0.3的钽铌酸镓镧(LGNT)固溶体晶体的非线性光学系数对比。
图3附图为本发明实施例2提供的Nb 5+/Ta 5+比例为0.9:0.1，0.7:0.3的钽铌酸镓镧(LGNT)固溶体晶体与铌酸镓镧(LGN)晶体和钽酸镓镧(LGT)晶体的Ⅰ类相位匹配调谐曲线对比。
图4附图为本发明实施例2提供的Nb 5+/Ta 5+比例为0.9:0.1，0.7:0.3的钽铌酸镓镧(LGNT)固溶体晶体与铌酸镓镧(LGN)晶体和钽酸镓镧(LGT)晶体的Ⅱ类相位匹配调谐曲线对比。
图5附图为本发明提供的硅酸镓镧族晶体A 3BC 3D 2O 14的结构示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而 不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例公开了一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，其特征在于，硅酸镓镧族晶体A 3BC 3D 2O 14主要包括铌酸镓镧(LGN)晶体、钽酸镓镧(LGT)晶体、硅酸镓镧(LGS)晶体等，通过调节同结构的硅酸镓镧族晶体组分比例形成固溶体晶体，使得不同的离子在多面体基团中进行混占，改变固溶体晶体的多面体格位结构、畸变程度、折射率和折射色散。
为进一步优化上述技术方案，通过将晶体结构相同、组分相近的铌酸镓镧晶体、钽酸镓镧晶体或硅酸镓镧晶体按不同比例进行互溶，形成固溶体晶体，使得硅酸镓镧族晶体的B位和/或D位结构改变。
为进一步优化上述技术方案，B位基团采取Ga 3+、Nb 5+、Ta 5+、Ti 4+、Zr 4+、Hf 4+、Sn 4+、Sb 5+等离子混占。
为进一步优化上述技术方案，D位基团采取Ga 3+、Ge 4+、Si 4+等离子混占。
为进一步优化上述技术方案，同时在B位和D位两类多面体基团中采取不同离子进行混占，在B位采取Ga 3+、Zr 4+离子混占，D位采取Ga 3+、Si 4+离子混占，进而形成锆硅酸镓镧固溶体晶体。
提供的非线性光学晶体为硅酸镓镧族的钽铌酸镓镧固溶体晶体，其化学式为La 3Ga 5.5(Nb 1-xTa x) 0.5O 14，属于三方晶系，32点群，存在一类(入射的两束光偏振方式一致，均为e光)及二类相位匹配(入射的两束光偏振方向不一致，一束为o光，一束为e光)，相对应的有效二阶非线性系数为
Figure PCTCN2022114468-appb-000001
(一类位相匹配)及
Figure PCTCN2022114468-appb-000002
(二类位相匹配)，θ为相位匹配角度，
Figure PCTCN2022114468-appb-000003
为方位角。B位基团容纳Ga 3+、Nb 5+、Ta 5+、Ti 4+、Zr 4+、Hf 4+、Sn 4+、Sb 5+等多种离子，采用不同的离子混占的方式，能增大B位基团的畸变度，增大非线性光学系数；同时不同离子的电子云结构存在一定的差异，可以调节晶体的折射率和折射率色散，减小相位匹配角度，进而增大有效非线性光学系数。另外Ga 3+、Nb 5+、Ta 5+、Ti 4+、Zr 4+、Hf 4+、Sn 4+、Sb 5+等多种离子的离子半径相近，具有较好的晶格匹配度，可以形成无限固溶体晶体，易获得高光学质量大尺寸单晶。同时D位基团也可容纳多种离子，如Ga 3+、Ge 4+、Si 4+。
实施例1：以铌酸镓镧(LGN)晶体和钽酸镓镧(LGT)晶体所能形成的钽铌酸镓镧(LGNT)固溶体晶体为例，我们设计了Nb 5+/Ta 5+比例为0.5:0.5的钽铌酸镓镧(LGNT)固溶体晶体，其具体的La 2O 3，Ga 2O 3，Nb 2O 5，Ta 2O 5四种原料的摩尔比为0.3:0.55:0.025:0.025。该晶体同属于三方晶系、32点群，随着Nb 5+/Ta 5+组分比例的变化，B位基团的畸变度增大，有利于增大非线性光学系数；同时晶体折射率和折射率色散大小随之发生改变，可以减小相位匹配角度，有利于增大晶体的有效非线性光学系数。
实施例2：我们设计以下不同Nb 5+/Ta 5+占比的钽铌酸镓镧(LGNT)固溶体晶体，如Nb 5+/Ta 5+比例为0.9:0.1、0.7:0.3、0.3:0.7、0.1:0.9等不同Nb 5+/Ta 5+比例的钽铌酸镓镧(LGNT)固溶体晶体，其具体的La 2O 3，Ga 2O 3，Nb 2O 5，Ta 2O 5四种原料的摩尔比可以为0.3:0.55:0.045:0.005、0.3:0.55:0.035:0.015、0.3:0.55:0.015:0.035、0.3:0.55:0.005:0.045。该系列固溶体晶体同样保持了铌酸 镓镧(LGN)和钽酸镓镧(LGT)的晶体结构，可以连续地调节该族晶体的折射率，进而改变相位匹配角度，增大有效非线性光学系数。
实施例3：以锆酸镓镧(LGZr)和硅酸镓镧(LGS)所能形成的锆硅酸镓镧(LZGS)固溶体晶体为例，我们可以设计Zr 4+/Si 4+比例为0.5:0.5的La 3Zr 0.5Ga 5Si 0.5O 14晶体，其具体的四种原料La 2O 3，Ga 2O 3，ZrO 2，SiO 2的摩尔比为0.3:0.5:0.1:0.1。该晶体属于三方晶系、32点群，B位和D位分别采取Ga 3+/Zr 4+和Ga 3+/Si 4+两种离子共占，B位基团和D位基团的畸变度增大，有利于增大非线性光学系数；同时晶体折射率和折射率色散大小随之发生改变，可以减小相位匹配角度，有利于增大晶体的有效非线性光学系数。
实施例4：以锆酸镓镧(LGZr)和硅酸镓镧(LGS)所能形成的锆硅酸镓镧(LZGS)固溶体晶体为例，我们可以设计不同Zr 4+/Si 4+比例的锆硅酸镓镧(LZGS)固溶体晶体，如Zr 4+/Si 4+比例为0.9:0.1、0.7:0.3、0.3:0.7、0.1:0.9等不同比例的固溶体晶体，其中La 2O 3，Ga 2O 3，ZrO 2，SiO 2四种原料的摩尔比可以为0.3:0.5:0.18:0.02、0.3:0.5:0.14:0.06、0.3:0.5:0.06:0.14、0.3:0.5:0.02:0.18。该系列晶体同样属于三方晶系、32点群，B位和D位分别采取Ga 3+/Zr 4+和Ga 3+/Si 4+两种离子共占，使B位基团和D位基团的畸变度增大，有利于增大非线性光学系数；同时调节晶体的折射率和折射率色散，可以减小相位匹配角度，有利于增大晶体的有效非线性光学系数。
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。 对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (5)

  1. 一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，其特征在于，硅酸镓镧族晶体A 3BC 3D 2O 14主要包括铌酸镓镧LGN晶体、钽酸镓镧LGT晶体、硅酸镓镧LGS晶体，通过调节同结构的硅酸镓镧族晶体组分比例形成固溶体晶体，使得不同的离子在多面体基团中进行混占，改变固溶体晶体的多面体格位结构、畸变程度、折射率和折射色散。
  2. 根据权利要求1所述的一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，其特征在于，通过将晶体结构相同、组分相近的铌酸镓镧晶体、钽酸镓镧晶体或硅酸镓镧晶体按不同比例进行互溶，形成固溶体晶体，使得硅酸镓镧族晶体的B位和/或D位结构改变。
  3. 根据权利要求1所述的一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，其特征在于，B位基团采取Ga 3+、Nb 5+、Ta 5+、Ti 4+、Zr 4+、Hf 4+、Sn 4+、Sb 5+离子混占。
  4. 根据权利要求1所述的一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，其特征在于，D位基团采取Ga 3+、Ge 4+、Si 4+离子混占。
  5. 根据权利要求1所述的一种硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法，其特征在于，同时在B位和D位两类多面体基团中采取不同离子进行混占，在B位采取Ga 3+、Zr 4+离子混占，D位采取Ga 3+、Si 4+离子混占，进而形成锆硅酸镓镧固溶体晶体。
PCT/CN2022/114468 2022-08-17 2022-08-24 硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法 Ceased WO2024036655A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/953,362 US12436316B2 (en) 2022-08-17 2022-09-27 Effective nonlinear optical coefficient optimization method for langasite group solid solution crystals

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210986346.8 2022-08-17
CN202210986346.8A CN115185137B (zh) 2022-08-17 2022-08-17 硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/953,362 Continuation-In-Part US12436316B2 (en) 2022-08-17 2022-09-27 Effective nonlinear optical coefficient optimization method for langasite group solid solution crystals

Publications (1)

Publication Number Publication Date
WO2024036655A1 true WO2024036655A1 (zh) 2024-02-22

Family

ID=83524184

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/114468 Ceased WO2024036655A1 (zh) 2022-08-17 2022-08-24 硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法

Country Status (2)

Country Link
CN (1) CN115185137B (zh)
WO (1) WO2024036655A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117305982B (zh) * 2023-10-10 2024-11-22 山东大学 一种新型硅酸镓镧族晶体及其电光系数优化方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000341078A (ja) * 1999-05-31 2000-12-08 Kyocera Corp 圧電振動子
JP2002338394A (ja) * 2001-05-15 2002-11-27 Victor Co Of Japan Ltd ランガサイト型結晶薄膜及びその製造方法
CN1402391A (zh) * 2002-05-20 2003-03-12 山东大学 一种晶体电光q开关器件
CN101190798A (zh) * 2006-11-29 2008-06-04 山东大学 铌酸镓镧系列纳米粉体的制备方法
CN101275278A (zh) * 2007-12-28 2008-10-01 中国科学院上海硅酸盐研究所 一种硅酸镓锑基压电单晶
CN104695018A (zh) * 2013-12-05 2015-06-10 中国科学院上海硅酸盐研究所 一种硅酸铝镓钽钙压电晶体及其制备方法
CN109518270A (zh) * 2018-10-10 2019-03-26 同济大学 一种单晶光纤的包层制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001080988A (ja) * 1999-09-07 2001-03-27 Kinya Adachi 固溶体系結晶及び育成方法
CN101896429B (zh) * 2007-12-10 2012-07-18 旭硝子株式会社 氧化铈-氧化锆类固溶体结晶微粒及其制造方法
WO2012122686A1 (zh) * 2011-03-15 2012-09-20 中国科学院物理研究所 氟化硫酸铁盐化合物、制备方法及用途

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000341078A (ja) * 1999-05-31 2000-12-08 Kyocera Corp 圧電振動子
JP2002338394A (ja) * 2001-05-15 2002-11-27 Victor Co Of Japan Ltd ランガサイト型結晶薄膜及びその製造方法
CN1402391A (zh) * 2002-05-20 2003-03-12 山东大学 一种晶体电光q开关器件
CN101190798A (zh) * 2006-11-29 2008-06-04 山东大学 铌酸镓镧系列纳米粉体的制备方法
CN101275278A (zh) * 2007-12-28 2008-10-01 中国科学院上海硅酸盐研究所 一种硅酸镓锑基压电单晶
CN104695018A (zh) * 2013-12-05 2015-06-10 中国科学院上海硅酸盐研究所 一种硅酸铝镓钽钙压电晶体及其制备方法
CN109518270A (zh) * 2018-10-10 2019-03-26 同济大学 一种单晶光纤的包层制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIANG FEI, LIN ZHE-SHUAI, WU YI-CHENG: "First principle study of nonlinear optical crystals", ACTA PHYSICA SINICA, vol. 67, no. 11, 1 January 2018 (2018-01-01), pages 114203, XP093140108, ISSN: 1000-3290, DOI: 10.7498/aps.67.20180189 *

Also Published As

Publication number Publication date
CN115185137B (zh) 2024-10-08
CN115185137A (zh) 2022-10-14

Similar Documents

Publication Publication Date Title
DE102018105290B4 (de) Schichtsystem, Herstellungsverfahren und auf dem Schichtsystem ausgebildetet SAW-Bauelement
Taleb et al. Physical investigations of nanophotonic LiNbO3 films for photonic applications
CN115185137B (zh) 硅酸镓镧族固溶体晶体的有效非线性光学系数优化方法
CN107272216A (zh) 透射式金属超材料光束偏振分布变换器件
DE69033660T2 (de) Dünnfilmeinzelkristall aus lithiumniobat und verfahren zu seiner herstellung
JP3148896B2 (ja) ニオブ酸リチウム単結晶薄膜
US12436316B2 (en) Effective nonlinear optical coefficient optimization method for langasite group solid solution crystals
US6625186B1 (en) Laser frequency doubling device of ReCa4O(BO3)3 crystal with specific cut angles
CN109217842A (zh) 近零温度系数的声表面波滤波器及其制备方法
CN115509047B (zh) 圆偏振切换装置及其优化方法
CN108683072B (zh) 一种提高sbo深紫外倍频激光输出效率的方法
JP2008233403A (ja) 反射防止膜及びこれを有する光学部品
CN115390185B (zh) 一种采用扶手椅边界的谷边缘态波导及其应用
CN118164848A (zh) 化合物硝酸草酸羟基氟化硼酸钾及硝酸草酸羟基氟化硼酸钾双折射晶体及制备方法和用途
CN106521628B (zh) 氟钒酸铅双折射晶体及其制备方法和应用
Ye et al. Direct growth of lithium niobate thin films for acoustic resonators
KR100439960B1 (ko) 열확산법을 이용한리드마그네슘니오베이트-리드티타네이트 광도파로 및 그의제조방법
CN104950385A (zh) 方柱式正方晶格光子晶体高折射率双补偿散射柱直角波导
CN119065173B (zh) 非线性光学晶体连续波变频器件、其工作方法及制备方法
CN1779507A (zh) 光元件和光转换器
JPH0566315A (ja) ＬｉＮｂＯ３ 薄膜光導波路装置とその製法
CN119335767A (zh) 带电介质薄膜的基板、光波导元件和光调制元件
JP2945107B2 (ja) 光波長変換素子及びその製造方法
JPH0269395A (ja) リチウム酸化物系単結晶薄膜の製法
WO2022038676A1 (ja) アモルファス半導体薄膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22955434

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22955434

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 21.07.2025)

122 Ep: pct application non-entry in european phase

Ref document number: 22955434

Country of ref document: EP

Kind code of ref document: A1