WO2020211333A1 - 嵌入式晶体及其制备方法和应用 - Google Patents

嵌入式晶体及其制备方法和应用 Download PDF

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WO2020211333A1
WO2020211333A1 PCT/CN2019/115696 CN2019115696W WO2020211333A1 WO 2020211333 A1 WO2020211333 A1 WO 2020211333A1 CN 2019115696 W CN2019115696 W CN 2019115696W WO 2020211333 A1 WO2020211333 A1 WO 2020211333A1
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crystal
embedded
nanocrystal
source
main matrix
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PCT/CN2019/115696
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English (en)
French (fr)
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钟海政
陈小梅
路文高
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致晶科技（北京）有限公司
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Publication of WO2020211333A1 publication Critical patent/WO2020211333A1/zh

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the application relates to an embedded crystal and its preparation method and application, belonging to the field of optical technology.
  • the optical phase retarder is one of the important devices to realize the optical phase modulation and the conversion of the optical polarization state.
  • the achromatic phase retarder weakens the dependence of the phase retardation on the wavelength, and can be used in a larger spectral range, so it is used in spectral shaping , Laser tuning and optical communication have broad application prospects.
  • the achromatic phase retarders on the market are divided into two types: birefringent type and metamaterial type based on helical antenna theory according to different design mechanisms. These two types generally have low delay accuracy, low achromatic degree, complex structure, and comparison of operation. Disadvantages such as trouble, and need to go through fine optical design during production.
  • the traditional achromatic phase retarder is an achromatic wave plate composed of more than two pieces of the same material or different kinds of materials, and its achromatic wavelength depends on the allowable error of achromaticity.
  • the disadvantages of traditional achromatic phase retarders are: (1) need multiple crystals, which consumes a lot of material cost; (2) need to go through fine optical design; (3) the adjustable band is narrow, about ⁇ of the center wavelength 150nm.
  • Metamaterials are materials with periodic structures that are processed by micro-nano materials. Because the nature of metamaterials usually has circular dichroism, the Fabry-Perot resonant cavity (FP cavity) formed by superimposing light beams on the metamaterial substance is based on circular dichroism. ) Oscillates back and forth, and wide bandwidth polarization conversion from linearly polarized light to circularly polarized light can be realized by changing the optical path difference.
  • FP cavity Fabry-Perot resonant cavity
  • the present invention provides an embedded crystal.
  • the crystal has a structure of "nanocrystal embedded in the main matrix crystal", which can achieve the performance of an achromatic quarter wave plate in a single crystal.
  • the embedded crystal includes a nanocrystal and a main matrix crystal.
  • the nanocrystal is embedded in the main matrix crystal and distributed on a certain crystal surface of the main matrix crystal.
  • the size of the nanocrystals is 1 nm to 20 nm.
  • the upper limit of the nanocrystal size is independently selected from 2nm, 5nm, 10nm, 15nm, and 20nm; the lower limit of the nanocrystal size is independently selected from 1nm, 2nm, 5nm, 10nm, and 15nm.
  • the nanocrystals are selected from any one of crystal I with a perovskite structure, carbon dots, and MgF 2 .
  • MgF 2 is a tetragonal crystal system and belongs to a rutile crystal lattice.
  • the crystal I of the perovskite crystal structure is selected from any one of the compounds having the chemical formula shown in formula I;
  • B 1 is selected from at least one of Pb 2+ , Sn 2+ , Ge 2+ , Mn 2+ , Mo 2+ , Cu 2+ , and Sr 2+ ;
  • X 1 is selected from F -, Cl -, Br - in at least one - and I.
  • the material of the nanocrystal is any one selected from the group consisting of:
  • a material with the general structural formula ABX 3 where A is K, Rb or Cs, B is Pb, Sn, Ge, Mn, Mo, Cu or Sr, and X is one or two of F, Cl, Br and I;
  • the host matrix crystal is selected from at least one of crystal II having a perovskite structure, crystal having a sodium chloride structure, trisodium citrate, quartz, and mica.
  • the crystal II having a perovskite structure is selected from any one of compounds having the chemical formula shown in formula II;
  • B 2 is selected from at least one of Pb 2+ , Sn 2+ , Ge 2+ , Mn 2+ , Mg 2+ , Mo 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Ca 2+ , Sr 2+
  • X 2 is selected from F -, Cl -, Br - in at least one - and I.
  • the crystal having a cubic sodium chloride structure is selected from any one of compounds having the chemical formula shown in Formula III;
  • X 3 is selected from F -, Cl -, Br - in at least one - and I.
  • the material of the host matrix crystal is any item selected from the group consisting of:
  • the general structural formula is A 4 BX 6 material, where A is one or two of Na, K, Rb and Cs, and B is Pb, Sn, Ge, Mn, Mg, Mo, Cu, Zn, Cd, Ca or Sr; X is one or two of F, Cl, Br and I;
  • a method for preparing the embedded crystal described in any one of the above which is prepared by using method one, method two or method three;
  • the first method includes at least the following steps: heating and cooling the mixture containing the nanocrystal source and the main matrix crystal source, and in the cooling process, growing in situ to form the embedded crystal;
  • the second method includes at least the following steps: heating and cooling the mixture containing the nanocrystal source and the main matrix crystal source to form the main matrix crystal in the cooling process, and then through external control, the nanocrystal is formed in the main matrix crystal , To obtain the embedded crystal;
  • the external control includes any one of annealing treatment, laser irradiation, microwave vibration, and acoustic vibration;
  • the third solution includes at least the following steps: adding nanocrystals into a saturated solution of a host matrix crystal, cooling down, and embedding the nanocrystals in the host matrix crystal to obtain the embedded crystal.
  • the mixture containing the nanocrystal source and the main matrix crystal source is heated to 80-160°C and cooled to 20-30°C to obtain the embedded crystal.
  • the second method includes: heating the mixture containing the nanocrystal source and the main matrix crystal source to 140-160° C., cooling down to obtain the main matrix crystal, and then performing annealing treatment to obtain the embedded crystal;
  • the annealing conditions are as follows: annealing temperature 120-220°C; annealing time 5-6h.
  • the second method includes: heating the mixture containing the nanocrystalline source and the main matrix crystal source to 140-160° C., cooling down to obtain the main matrix crystal, and then performing laser irradiation treatment to obtain the embedded crystal;
  • the conditions of the laser irradiation treatment are: the laser wavelength is 600-1000 nm; the irradiation time is 4-6h.
  • the second method includes: heating the mixture containing the nanocrystalline source and the main matrix crystal source to 140-160°C, cooling down to obtain the main matrix crystal, and then placing it in a microwave vibration field or a sonic vibration field, and processing 7 ⁇ 10h, the embedded crystal is obtained.
  • the method for preparing embedded crystals for:
  • the nanocrystalline source includes A 1 X 1 and B 1 X 1 ;
  • the main matrix crystal source contains A 2 X 2 and B 2 X 2 ;
  • a 1 and A 2 are selected from the same element; B 1 and B 2 are selected from the same element; X 1 and X 2 are selected from the same element.
  • the embedded The preparation method of type crystal is:
  • the nanocrystalline source includes urea
  • the main matrix crystal source includes trisodium citrate.
  • the method for preparing embedded crystals for:
  • the external control includes any one of annealing treatment, laser irradiation, microwave vibration, sonic vibration, and pressure treatment;
  • the nanocrystalline source includes A 1 X 1 and B 1 X 1 ;
  • the main matrix crystal source contains A 2 X 2 and B 2 X 2 ;
  • a 1 and A 2 are selected from the same element; B 1 and B 2 are selected from the same element; X 1 and X 2 are selected from the same element.
  • the host matrix crystals and nanocrystals are both perovskite-type structures, and the element composition of the host matrix crystals is different from that of the nanocrystals, the embedded crystals
  • the preparation method is:
  • the external control includes any one of annealing treatment, laser irradiation, microwave vibration, sonic vibration, and pressure treatment;
  • the source comprises nanocrystals CH 3 NH 3 PbBr 3, CH 3 NH 3 PbCl 3, CH any one of the 3 3 PbI 3 NH;
  • the main matrix crystal source contains A 2 X 2 and B 2 X 2 .
  • the preparation method of the embedded crystal is:
  • nanocrystals Adding nanocrystals to a solution containing host matrix crystals and cooling, the nanocrystals are embedded in the host matrix crystals to obtain the embedded crystals;
  • the nanocrystals include any one of MgF 2 , CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbCl 3 , and CH 3 NH 3 PbI 3 ;
  • the host matrix crystal includes any one of sodium chloride, NaNO 3 , sodium bromide, and sodium iodide.
  • the in-situ embedding method artificially increases the ratio of X 1 , X 2 , and X 3 when growing the embedded crystal configuration solution, such as choosing to contain (X 1 ) - , (X 2 ) - , (X 3 ) - ionic or pay more a 1, a 2, a 3 and the like.
  • selecting comprises (X 1) -, (X 2) -, (X 3) - the solvent ions, a solution of X 1, X 2, X moles of 3 with respect to A 2 4 B 2 X 2 6 over -30 times;
  • X 1- assumption here is defined as Cl -, the selected solvent or HCl dichloro carbon, trichloride, carbon tetrachloride ((X 1) -, ( X 2) -, (X 3) - ion Solvent).
  • the raw materials such as PbCl 2 are artificially added more than CH 3 NH 3 Cl instead of adding raw materials in an equimolar ratio (add more A 1 , A 2 , A 3 etc.).
  • the crystal is made by forming nanocrystals in a post-adjusted manner after the host matrix crystal is grown.
  • the post-stage adjustment method includes: high-energy laser, X-ray or electron beam irradiation, or high-temperature heating, pressure, or ultrasonic vibration to apply energy to the host matrix crystal, so that Nanocrystals are formed in the structure of the matrix crystals.
  • an achromatic phase retarder comprising the embedded crystal of any one of the above and/or the preparation method of any one of the above Any of the embedded crystals.
  • the host matrix crystal is a transparent crystal
  • the refractive index of the host matrix crystal is less than 2;
  • the band gap of the host matrix crystal is greater than 2.5 eV.
  • the refractive index of the host matrix crystal is less than 1.8.
  • the embedded crystal is a disc with a diameter of 0.5-100 cm and a thickness of 0.01-1 cm.
  • the upper limit of the diameter of the embedded crystal is independently selected from 1.0cm, 1.5cm, 2.0cm, 2.5cm, 3.0cm, and 100cm; the lower limit of the diameter of the embedded crystal is independently selected from 0.5cm, 1.0cm, 1.5cm, 2.0cm , 2.5cm, 3.0cm.
  • the upper limit of the thickness of the embedded crystal is independently selected from 0.2cm, 0.25cm, 0.3cm, 0.4cm, and 1cm; the lower limit of the thickness of the embedded crystal is independently selected from 0.01cm, 0.1cm, 0.2cm, 0.25cm, 0.3cm , 0.4cm.
  • the absolute value of the refractive index difference ⁇ n between the host matrix crystal and the nanocrystal is in the range of 0.15 ⁇ n ⁇ 2.00.
  • the upper limit of the absolute value range of ⁇ n is independently selected from 0.5, 1.0, 1.5, and 2.00; the lower limit of the absolute value range of ⁇ n is independently selected from 0.15, 0.5 , 1.0, 1.5.
  • this application provides an achromatic phase retarder made of crystals, wherein: the structure of the crystal is nanocrystals embedded in the host matrix crystal; the size of the nanocrystals is 1nm-20nm and is The main matrix crystal is distributed in one crystal plane; the main matrix crystal is a transparent single crystal with a refractive index less than 2 and a band gap greater than 2.5 eV; and for light with a wavelength of 400 nm to 3000 nm, the main matrix crystal and the nanocrystal
  • the range of the refractive index difference ⁇ n is 0.15 ⁇ n ⁇ 2.00, wherein the achromatic retarder is a crystal plate with a thickness of 0.1cm to 0.4cm.
  • the refractive index of the host matrix crystal is less than 1.8.
  • the phase retarder is a disc with a diameter of 0.5 cm to 3 cm.
  • the applicable wavelength of the phase retarder is 400 nm to 3000 nm.
  • carbon dots refer to carbon-based zero-dimensional materials, which have no fixed molecular formula and structure, and their size is usually below 10 nm.
  • the present invention innovatively discovers the properties of the achromatic phase retardation of the crystal with the structure of "nanocrystal embedded in the host matrix crystal", so that the achromatic phase retarder is made by using this property of this crystal, instead of the previous multiple wafer composite
  • the composite wave plate composed of multiple crystals can achieve the effect of changing the wide band from linearly polarized light to circularly polarized light, and the retardation accuracy is high, which reduces the tedious and difficult preparation of phase retarders, optical path adjustment and device assembly processes The difficulty of this greatly improves the stability of the light polarization state.
  • the present invention provides an achromatic phase retarder made of crystals and a manufacturing method. Starting from the structure design of crystal materials, the present invention forms a new crystal by embedding nanocrystals in single crystals, and finally only single crystals are used. This crystal realizes the full performance of an achromatic quarter-wave plate, which can retard the optical phase of the ultra-wide band from visible light to infrared (400nm ⁇ 3000nm) Phase difference The light is adjusted to ⁇ or its integer multiples, which avoids the cumbersome process and optical design process of the existing wide-band achromatic waveplates that need to adhere multiple and multiple crystals.
  • the design process of the existing achromatic phase retarder often affects the technical requirements of the phase retarder such as the width of the applicable band and the delay accuracy.
  • the achromatic phase retarder provided by the present invention eliminates these adverse effects from the source and uses adjustments. Convenient, greatly reducing the difficulty of optical path adjustment and device assembly process, and improving the coupling of optical components, optical communication performance and optical path stability.
  • FIG. 1 is a schematic structural diagram of an embedded crystal in a possible implementation manner of this application
  • FIG. 3 is a scanning electron microscope test diagram of the embedded crystal in a possible implementation of this application.
  • FIG. 5 is an effective band gap test diagram of an achromatic phase retarder in a possible implementation manner of this application
  • FIG. 6a shows the effect of the wide band of 530 nm to 800 nm being controlled by the achromatic phase retarder when the angle between the vibration direction of the linearly polarized light and the crystal plane is ⁇ ° in a possible implementation of this application;
  • Figure 6b is a possible implementation of this application when the angle between the vibration direction of linearly polarized light and the crystal plane is When the wide band of 530nm ⁇ 800nm is adjusted by the achromatic phase retarder;
  • Figure 6c is a possible implementation of this application when the angle between the vibration direction of linearly polarized light and the crystal plane is When the wide band of 530nm ⁇ 800nm is adjusted by the achromatic phase retarder.
  • the JEOL-JEM 2100F Transmission Electron Microscopy operating at an acceleration voltage of 200kV instrument is used for structural characterization
  • the morphology characterization adopts EOS 500D Cannon camera instrument
  • the refractive index test adopts ES01-M fast spectroscopic spectral ellipsometer (Ellitop Scientific Co., Ltd., China) instrument;
  • the present invention provides an embedded crystal.
  • the structure of the crystal is "nanocrystal embedded in the main matrix crystal"; the size of the nanocrystal is 1nm-20nm and is distributed in one crystal plane of the main matrix crystal; the main matrix crystal has a refractive index less than 2 and a band gap greater than 2.5 eV Transparent single crystal; and for light with a wavelength of 400 nm to 3000 nm, the range of the refractive index difference between the host matrix crystal and the nanocrystal is 0.15 to 2.00.
  • the achromatic retarder is a crystal plate with a thickness of 0.1 cm to 0.4 cm.
  • FIG. 1 are respectively schematic diagrams of nanocrystals embedded in the crystal structure of the host matrix along the x, y, and z directions in a possible implementation manner of the present invention. As shown in Figure 1, the darker inner part of the figure is embedded perovskite-type nanocrystals, and the lighter outer part is perovskite-type host matrix crystals.
  • the lighter outer part in Figure 1a The similar circles in belong to the isolated ⁇ B 2 X 2 6 ⁇ 4- octahedron in the crystal structure of the main matrix, the other gray atoms represent A 2 , and the inner dark part represents the corners shared by the nanocrystal structure ⁇ B 1 X 1 6 ⁇ 4- octahedron, the small sphere between the large sphere and the large sphere represents A 1 .
  • the wide band gap transparent single crystal is a single crystal with a band gap greater than 2.5 eV. When the band gap of the single crystal is greater than 2.5 eV, the single crystal will be transparent or greenish or blueish transparent.
  • the material of the nanocrystals is different from the material of the host matrix crystal, and the nanocrystals are distributed in one crystal plane of the host matrix crystal.
  • Nanocrystals are nanoparticles with a size of about 1 nm to 20 nm, and their refractive index is not equal to the refractive index of the host matrix crystal, that is, the refractive index of the nanocrystal is greater than or less than the refractive index of the host matrix crystal.
  • the refractive index difference between the host matrix crystal and the nanocrystal is in the range of 0.15 to 2.00.
  • the range of the refractive index difference between the wide-band gap transparent single crystal and the nanocrystal is 0.15-2.00.
  • the material of the host matrix crystal is any one selected from the group consisting of:
  • the general structural formula is A 4 BX 6 material, where A is one or two of Na, K, Rb and Cs, and B is Pb, Sn, Ge, Mn, Mg, Mo, Cu, Zn, Cd, Ca or Sr; X is one or two of F, Cl, Br and I;
  • the material of the nanocrystal is any one selected from the group consisting of:
  • a material with the general structural formula ABX 3 where A is K, Rb or Cs, B is Pb, Sn, Ge, Mn, Mo, Cu or Sr, and X is one or two of F, Cl, Br and I;
  • a material with the general structural formula A 4 BX 6 is taken as an example, wherein when A is two of Na, K, Rb, and Cs, it refers to the structure A 4 in the general formula is composed of any two elements of Na, K, Rb and Cs, as long as the sum of the numerical subscripts of the chemical formulas of these two elements is equal to the numerical subscript of A 4 .
  • a 4 can be Na 2 K 2 , Rb 2 Cs 2 or Rb 3 K, and the corresponding general structure is Na 2 K 2 BX 6 , Rb 2 Cs 2 BX 6 or Rb 3 KBX 6 .
  • R and X are two of a plurality of elements, it is the same as the case of A above, and will not be repeated here.
  • the crystal with the structure of "nanocrystal embedded in the host matrix crystal” is formed in the following manner: the nanocrystal is embedded in the host matrix crystal in situ. That is, through the in-situ embedding method, when the crystal grows, a structure of the host matrix crystal containing nanocrystals is formed in-situ.
  • the crystals with the structure of "nanocrystals embedded in the host matrix crystals” can also be formed by the following method: after the host matrix crystals are grown, the nanocrystals are formed in a post-regulated manner. to make. The process is: irradiating with high-energy laser, X-ray, electron beam, etc., or applying energy to the main matrix crystal by high-temperature heating, pressure, or ultrasonic vibration, so that nanocrystals are formed in the structure of the main matrix crystal.
  • crystals with a structure of "nanocrystals embedded in host matrix crystals” can also be obtained in other ways, and the present invention is not limited to this.
  • the achromatic phase optical retarder made of crystal is a crystal plate with a thickness of 0.1 cm to 0.4 cm.
  • the crystals are sliced, polished, and made into crystal sheets with a thickness of 0.1 cm to 0.4 cm. Only one piece of this crystal plate can realize the full performance of an achromatic quarter-wave plate.
  • slicing refers to cutting into pieces using a blade, laser, etc.
  • Grinding and polishing refers to the use of polishing powder or polishing paste on sandpaper, nylon cloth, wool cloth, fiber, flocking wool or silk to polish the crystal sheet until the surface is mirror smooth.
  • the achromatic phase retarder made of crystals is a crystal disc with a diameter of 0.5 cm to 3 cm and a thickness of 0.1 cm to 0.4 cm.
  • the applicable wavelength range of the achromatic retarder made of crystal is 400 nm to 3000 nm. That is, for light of any wavelength in the 400nm-3000nm band, the achromatic phase retarder can realize the full performance of the achromatic quarter-wave plate. That is, the phase of the incident ray polarized light can be delayed Or will have The phase difference of circularly polarized light is adjusted to linearly polarized light with a phase difference of ⁇ or other integer multiples, or linearly polarized light is adjusted to circularly polarized light, which can realize the mutual conversion of linearly polarized light and circularly polarized light.
  • possible embodiments of the present invention also provide a method for making an achromatic phase retarder by using crystals.
  • the structure of the crystals is that nanocrystals are embedded in the main matrix crystal, and the size of the nanocrystals is 1nm-20nm and is in one Distributed in the crystal plane, the host matrix crystal is a transparent single crystal with a refractive index less than 2 and a band gap greater than 2.5 eV, and for light with a wavelength of 400 nm to 3000 nm, the refractive index difference between the host matrix crystal and the nanocrystal is in the range of 0.15 to 2.00.
  • the method includes:
  • the crystal is made into a disc with a diameter of 0.5 cm to 3 cm and a thickness of 0.1 cm to 0.4 cm.
  • the crystal is made by embedding the nanocrystal in situ into the host matrix crystal.
  • the crystal is made by forming nanocrystals in a post-adjustment manner after the host matrix crystal is grown.
  • the post-control methods include: high-energy laser, X-ray or electron beam irradiation, or high-temperature heating, pressure, or ultrasonic vibration to apply energy to the main matrix crystal, so that Nanocrystals are formed in the structure of the matrix crystals.
  • the present invention provides an achromatic phase retarder made of crystals and a manufacturing method.
  • the present invention starts from the structure design of crystal materials and forms a new crystal by embedding nanocrystals in a single crystal. In the end, only a single piece of this crystal is used to achieve the full performance of the achromatic quarter-wave plate, which can retard the optical phase of the ultra-wide band from visible light to infrared (400nm ⁇ 3000nm) Phase difference The light is adjusted to ⁇ or its integer multiples, which avoids the cumbersome process and optical design process of the existing wide-band achromatic waveplates that need to adhere multiple and multiple crystals.
  • the design process of the existing achromatic phase retarder often affects the technical requirements of the phase retarder such as the width of the applicable band and the delay accuracy.
  • the achromatic phase retarder provided by the present invention eliminates these adverse effects from the source and uses adjustments. Convenient, greatly reducing the difficulty of optical path adjustment and device assembly process, and improving the coupling of optical components, optical communication performance and optical path stability.
  • the crystals with carbon dots embedded in the main matrix of trisodium citrate dissolve 1g of trisodium citrate and 2g of urea in 10ml of N,N-dimethylformamide. Then the solution was transferred to an autoclave (in this application, the pressure of the autoclave can be 2MPa ⁇ 32MPa, specifically 5Mpa in this embodiment), and heated at 160°C for 4h, after which the reactor is naturally cooled to room temperature (30 °C), an embedded crystal with carbon dots embedded in the main matrix crystal of trisodium citrate was obtained, and it was recorded as 2# embedded crystal.
  • the pressure of the autoclave can be 2MPa ⁇ 32MPa, specifically 5Mpa in this embodiment
  • Example 1 Taking the sample in Example 1 as a typical representative, the CsPbCl 3 nanocrystals in Cs 4 PbCl 6 were tested by transmission electron microscopy.
  • the high resolution transmission electron microscopy test results are shown in Fig. 2.
  • Fig. 2 By comparing the lattice spacing and crystal system of Fig. 2 The comparison confirms that Fig. 2 shows that the nanocrystal is CsPbCl 3 , the main matrix crystal is Cs 4 PbCl 6 , and the nanocrystal CsPbCl 3 is embedded in the main matrix crystal Cs 4 PbCl 6 to form an embedded structure.
  • Example 1 Scanning electron microscopy tests were performed on the embedded crystals in Example 1 to Example 7, and the test results showed that the size of the nanocrystals was less than 20 nm.
  • Example 5 Taking the embedded crystal in Example 5 as a typical representative to perform a scanning electron microscope test, the test result is shown in Figure 3, which shows that the size of the nanocrystal is less than 20nm, and the small black dots in the figure are nanocrystals; Large gray dots are the main matrix.
  • Example 1 The embedded crystal in Example 1 was prepared (cut) into a wafer with a diameter of 0.5-3 cm and a thickness of 0.1-0.4 cm, and the surface roughness of the polished crystal was less than 1 nm, which was recorded as 1# achromatic phase retarder.
  • the method of preparing the achromatic phase retarder by the embedded crystals in Examples 2 to 7 is the same as the above, and will not be repeated here, and is respectively referred to as 2# ⁇ 7# achromatic phase retarder.
  • the 1# achromatic phase retarder is tested by Xenon lamp irradiation with the refractive index of the main matrix crystal Cs 4 PbCl 6 and nanocrystalline CsPbCl 3 in the visible light region.
  • the test result is shown in Figure 4, which shows that the crystal is in The effective refractive index in the 550-800nm band is between 1.749-1.735.
  • Fig. 6a, Fig. 6b and Fig. 6c respectively show when the angle between the vibration direction of linearly polarized light and the crystal plane is with
  • the effect picture after 530nm ⁇ 800nm wide-band light is regulated by 1# achromatic phase retarder, where It can be any angle.
  • achromatic phase retarder 1# achromatic phase retarder
  • the vertical axis shows this effect in the 530nm ⁇ 800nm band.

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Abstract

一种嵌入式晶体及其制备方法和应用。该嵌入式晶体包括纳米晶和主基质晶体，该纳米晶嵌入该主基质晶体且分布于该主基质晶体的某一晶面。只用单片该晶体便实现了消色差四分之一波片的全部性能，避免了现有宽波段消色差波片需要粘连多个和多种晶体等繁琐的工艺及光学设计的过程。

Description

嵌入式晶体及其制备方法和应用 技术领域
本申请涉及一种嵌入式晶体及其制备方法和应用，属于光学技术领域。
背景技术
光学相位延迟器是实现对光相位调制及光偏振状态变换的重要器件之一，消色差相位延迟器因削弱了相位延迟量对波长的依赖程度，可用于较大的光谱范围，因此在光谱整形、激光调谐和光通信等领域都有着广泛的应用前景。目前市场上的消色差相位延迟器根据设计机理的不同有双折射型和基于螺旋天线理论的超材料型两类，这两类普遍存在延迟精度较低、消色差度低、结构复杂、操作比较麻烦等缺点，且生产时需要经过精细的光学设计。
具体来说，传统的消色差相位延迟器是两片以上的同种材料或不同种材料组成的消色差波片，其消色差的波长取决于消色性的允许误差。然而，若想达到较宽的允许波段，通常需要六片不同种材料粘连而成。传统的消色差相位延迟器的缺点是：(1)需要多片晶体，耗费的材料成本大；(2)需要经过精细的光学设计；(3)能调控的波段较窄，约中心波长的±150nm。
相比于传统的消色差相位延迟器，现有技术中还提出了一种采用超材料制成的宽波段光学相位延迟器。超材料是经微纳加工的具有周期性结构的材料，因超材料本质通常具有圆二色性，在圆二色性的基础上叠加光束在超材料物质形成的Fabry-Perot谐振腔(F-P腔)中来回震荡，通过改变光程差可以实现线偏振光到圆偏振光的宽带宽偏振转换。上述的宽波段光学相位延迟器虽然适用于宽波段，但是存在以下缺点：(1)制备复杂；(2)超材料因加工精度极限，目前只能实现对红外波段的调控。
因此，目前亟须一种结构简单、制备简便、延迟精度高且适用于宽波段的消色差相位延迟器。
发明内容
为此，本发明提供了一种嵌入式晶体，通过对晶体的结构设计，使得晶体具有“纳米晶嵌入主基质晶体”结构，可以达到一片晶体具备消色差四分之一波片的性能。
一种嵌入式晶体，所述嵌入式晶体包括纳米晶和主基质晶体，所述纳米晶嵌入所述主基质晶体且分布于所述主基质晶体的某一晶面。
可选地，所述纳米晶的尺寸为1nm～20nm。
具体地，纳米晶尺寸的上限独立地选自2nm、5nm、10nm、15nm、20nm；纳米晶尺寸的下限独立地选自1nm、2nm、5nm、10nm、15nm。
可选地，所述纳米晶选自具有钙钛矿结构的晶体Ⅰ、碳点、MgF 2中的任一种。MgF 2为四方晶系，属于金红石型晶格。
可选地，所述钙钛矿晶体结构的晶体Ⅰ选自具有式Ⅰ所示化学式的化合物中的任一种；
A 1B 1X 1 3  式Ⅰ
其中，A 1选自K +、Rb +、Cs +、CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +中的至少一种，n为整数，n的取值范围为0≤n≤3；
B 1选自Pb 2+、Sn 2+、Ge 2+、Mn 2+、Mo 2+、Cu 2+、Sr 2+中的至少一种；
X 1选自F -、Cl -、Br -和I -中的至少一种。
具体地，所述纳米晶的材料是从包括以下项的组中选择的任一项：
结构通式为ABX 3的材料，其中A为K、Rb或Cs，B为Pb、Sn、Ge、Mn、Mo、Cu或Sr，X为F、Cl、Br和I中的一个或两个；
结构通式为RBX 3的材料，其中R为CH 3(CH 2) nNH 3 +或NH＝CHNH 3 +，其中n＝0至3，B为Pb、Sn、Ge、Mn、Mo、Cu或Sr，X为F、Cl、Br和I中的一个或两个；
碳点；以及MgF。
可选地，所述主基质晶体选自具有钙钛矿结构的晶体Ⅱ、具有 氯化钠结构的晶体、柠檬酸三钠、石英、云母中的至少一种。
可选地，所述具有钙钛矿结构的晶体Ⅱ选自具有式Ⅱ所示化学式的化合物中的任一种；
A 2 4B 2X 2 6         式Ⅱ
其中，A 2选自Na +、K +、Rb +、Cs +、CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +、C 6H 5(CH 2) nNH 2 +中的至少一种，n为整数，n的取值范围为0≤n≤10；
B 2选自Pb 2+、Sn 2+、Ge 2+、Mn 2+、Mg 2+、Mo 2+、Cu 2+、Zn 2+、Cd 2+、Ca 2+、Sr 2+中的至少一种；
X 2选自F -、Cl -、Br -和I -中的至少一种。
可选地，所述具有立方晶系氯化钠结构的晶体选自具有式Ⅲ所示化学式的化合物中的任一种；
A 3X 3        式Ⅲ
其中，A 3选自Na +、K +、Rb +、Cs +、CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +、C 6H 5(CH 2) nNH 2 +中的至少一种，n为整数，n的取值范围为0≤n≤10；
X 3选自F -、Cl -、Br -和I -中的至少一种。
具体地，所述主基质晶体的材料是从包括以下项的组中选择的任一项：
结构通式为A 4BX 6的材料，其中A为Na、K、Rb和Cs中的一个或两个，B为Pb、Sn、Ge、Mn、Mg、Mo、Cu、Zn、Cd、Ca或Sr；X为F、Cl、Br和I中的一个或两个；
结构通式为R 4BX 6的材料，其中R为CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +和C 6H 5(CH 2) nNH 2 +中的一个或两个，其中n＝0至10，B为Pb、Sn、Ge、Mn、Mg、Mo、Cu、Zn、Cd、Ca或Sr，X为F、Cl、Br和I中的一个或两个；
结构通式为AX的材料，其中A为Na、K、Rb或Cs；X为F、Cl、Br或I；
结构通式为RX的材料，其中R为CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +或C 6H 5(CH 2) nNH 2，其中n＝0至10；X为F、 Cl、Br或I；
柠檬酸三钠Na 3C 6H 5O 7·2H 2O；
石英；以及云母。
根据本申请的一方面，提供了上述任一项所述嵌入式晶体的制备方法，采用方法一、方法二或者方法三制备得到；
所述方法一至少包括以下步骤：将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中，原位生长形成所述嵌入式晶体；
所述方法二至少包括以下步骤：将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中形成主基质晶体，之后经过外界调控，在所述主基质晶体中形成纳米晶，得到所述嵌入式晶体；
其中，所述外界调控包括退火处理、激光辐照、微波振动、声波振动中的任一种；
所述方案三至少包括以下步骤：将纳米晶加入主基质晶体的饱和溶液中，降温，所述纳米晶嵌入所述主基质晶体中，得到所述嵌入式晶体。
可选地，在所述方法一中，将所述含有纳米晶源和主基质晶体源的混合物加热至80～160℃，降温至20～30℃，得到所述嵌入式晶体。
可选地，所述方法二包括：将含有纳米晶源和主基质晶体源的混合物加热至140～160℃，降温，得到主基质晶体，之后进行退火处理，得到嵌入式晶体；
所述退火处理的条件为：退火温度120～220℃；退火时间5～6h。
可选地，所述方法二包括：将含有纳米晶源和主基质晶体源的混合物加热至140～160℃，降温，得到主基质晶体，之后进行激光辐照处理，得到所述嵌入式晶体；
所述激光辐照处理的条件为：激光波长600～1000nm；辐照时间4～6h。
可选地，所述方法二包括：将含有纳米晶源和主基质晶体源的混合物加热至140～160℃，降温，得到主基质晶体，之后放置于微波振动场或声波振动场中，处理7～10h，得到所述嵌入式晶体。
在一种可能的原位生长的实施方式中，当主基质晶体和纳米晶均为钙钛矿型结构，且主基质晶体中的元素组成与纳米晶的元素组成相同时，嵌入型晶体的制备方法为：
所述将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中，原位形成所述嵌入式晶体；
其中，所述纳米晶源包括A 1X 1和B 1X 1；
所述主基质晶体源含有A 2X 2和B 2X 2；
A 1与A 2选自相同的元素；B 1和B 2选自相同的元素；X 1和X 2选自相同的元素。
在另一种可能的原位生长的实施方式中，在原位生长过程中，当主基质晶体和纳米晶为不同的晶体结构，且主基质晶体的元素组成与纳米晶的元素组成不同时，嵌入型晶体的制备方法为：
所述将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中，原位形成所述嵌入式晶体；
其中，所述纳米晶源包括尿素；
主基质晶体源包括柠檬酸三钠。
在一种可能的外界后期调控的实施方式中，当主基质晶体和纳米晶均为钙钛矿型结构，且主基质晶体中的元素组成与纳米晶的元素组成相同时，嵌入型晶体的制备方法为：
将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中形成主基质晶体，之后经过外界调控，在所述主基质晶体中形成纳米晶，得到所述嵌入式晶体；
其中，所述外界调控包括退火处理、激光辐照、微波振动、声波振动、加压处理中的任一种；
所述纳米晶源包括A 1X 1和B 1X 1；
所述主基质晶体源含有A 2X 2和B 2X 2；
A 1与A 2选自相同的元素；B 1和B 2选自相同的元素；X 1和X 2 选自相同的元素。
在另一种可能的外界后期调控的实施方式中，当主基质晶体和纳米晶均为钙钛矿型结构，且主基质晶体中的元素组成与纳米晶的元素组成不相同时，嵌入型晶体的制备方法为：
将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中形成主基质晶体，之后经过外界调控，在所述主基质晶体中形成纳米晶，得到所述嵌入式晶体；
其中，所述外界调控包括退火处理、激光辐照、微波振动、声波振动、加压处理中的任一种；
所述纳米晶源包括CH 3NH 3PbBr 3、CH 3NH 3PbCl 3、CH 3NH 3PbI 3中的任一种；
所述主基质晶体源含有A 2X 2和B 2X 2。
在一种可能的方法三的实施方式中，当主基质晶体和纳米晶为不同的晶体结构，且主基质晶体的元素组成与纳米晶的元素组成不同时，嵌入型晶体的制备方法为：
将纳米晶加入含有主基质晶体的溶液中，降温，所述纳米晶嵌入所述主基质晶体中，得到所述嵌入式晶体；
所述纳米晶包括MgF 2、CH 3NH 3PbBr 3、CH 3NH 3PbCl 3、CH 3NH 3PbI 3中的任一种；
所述主基质晶体包括氯化钠、NaNO 3、溴化钠、碘化钠中的任一种。
本申请中，原位嵌入方式，生长该嵌入式晶体配置溶液时人为的加大X 1，X 2，X 3的比例，如选择含有(X 1) ‐，(X 2) ‐，(X 3) ‐离子的溶剂或多加A 1,A 2,A 3等。
其中选择含有(X 1) ‐，(X 2) ‐，(X 3) ‐离子的溶剂时，溶液中X 1，X 2，X 3的摩尔数相对于A 2 4B 2X 2 6多1-30倍；
多加A 1,A 2,A 3时，X 1，X 2，X 3的摩尔比A 2 4B 2X 2 6多2-10倍。
假设这里X 1-限定为Cl -时，溶剂选择HCl或二氯化碳、三氯化碳、四氯化碳等((X 1) -，(X 2) -，(X 3) -离子的溶剂)。
或者原料里比如PbCl 2比CH 3NH 3Cl人为的多加，而不是等摩尔 比的添加原料(多加A 1,A 2,A 3等)。
在另一个实施例中，通过在生长出所述主基质晶体后以后期调控的方式形成纳米晶而制成所述晶体。
优选地，所述后期调控的方式包括：通过高能激光、X-射线或电子束进行辐照，或者通过高温加热、加压或超声波振动，对所述主基质晶体施加能量，使得在所述主基质晶体的结构中形成纳米晶。
根据本申请的又一方面，还提供了一种消色差相位延迟器，所述消色差相位延迟器包括上述任一项所述的嵌入式晶体和/或上述任一项所述的制备方法得到的嵌入式晶体中的任一种。
可选地，在所述嵌入式晶体中，所述主基质晶体为透明晶体；
所述主基质晶体的折射率小于2；
所述主基质晶体的带隙大于2.5eV。
优选地，所述主基质晶体的折射率小于1.8。
可选地，所述嵌入式晶体为直径0.5～100cm且厚度0.01～1cm的圆片。
嵌入式晶体的直径的上限独立地选自1.0cm、1.5cm、2.0cm、2.5cm、3.0cm、100cm；嵌入式晶体的直径的下限独立地选自0.5cm、1.0cm、1.5cm、2.0cm、2.5cm、3.0cm。
嵌入式晶体的厚度的上限独立地选自0.2cm、0.25cm、0.3cm、0.4cm、1cm；嵌入式晶体的厚度的下限独立地选自0.01cm、0.1cm、0.2cm、0.25cm、0.3cm、0.4cm。
可选地，在波长为400～3000nm的光照射下，所述主基质晶体与纳米晶的折射率差Δn的绝对值的取值范围为0.15≤∣Δn∣≤2.00。
在波长为400～3000nm的光照射下，Δn的绝对值的取值范围的上限独立地选自0.5、1.0、1.5、2.00；Δn的绝对值的取值范围的下限独立地选自0.15、0.5、1.0、1.5。
具体来说，本申请提供了一种利用晶体制成的消色差相位延迟器，其中：所述晶体的结构为纳米晶嵌入主基质晶体；所述纳米晶的尺寸为1nm～20nm并且在所述主基质晶体的一个晶面内分布；所述主基质晶体为折射率小于2、带隙大于2.5eV的透明单晶；并且对 于400nm～3000nm波长的光，所述主基质晶体与所述纳米晶的折射率差Δn的范围为0.15≤∣Δn∣≤2.00，其中，所述消色差相位延迟器是厚度为0.1cm～0.4cm的晶体片。
优选地，所述主基质晶体的折射率小于1.8。
优选地，所述相位延迟器是直径为0.5cm～3cm的圆片。
优选地，所述相位延迟器的适用波长为400nm～3000nm。
本申请中，“碳点”是指碳基零维材料，没有固定的分子式及结构，尺寸通常在10nm以下。
本发明创新地发现具有“纳米晶嵌入主基质晶体”结构的晶体在消色差相位延迟方面的性质，从而利用这种晶体的这种性质制作出消色差相位延迟器，代替了以往多个晶片复合组成的复合波片或要用多个晶体才能达到宽波段从线偏振光改性为圆偏振光的效果，且延迟精度高，降低了繁琐困难的相位延迟器的制备、光路调整及器件装配工艺的难度，大大改善了光的偏振态的稳定性。
本申请能产生的有益效果包括：
本发明提供了一种利用晶体制成的消色差相位延迟器和制作方法，本发明从晶体材料的结构设计出发，通过在单晶中嵌入纳米晶体形成了一种新的晶体，最终只用单片该晶体便实现了消色差四分之一波片的全部性能，可以将可见光至红外(400nm～3000nm)超宽波段的光相位延迟
Figure PCTCN2019115696-appb-000001
也可将此波段相位差
Figure PCTCN2019115696-appb-000002
的光调控成π或其整数倍，避免了现有宽波段消色差波片需要粘连多个和多种晶体等繁琐的工艺及光学设计的过程。
现有的消色差相位延迟器的设计过程往往影响着适用波段的宽窄、延迟精度等相位延迟器的技术要求，而本发明提供的消色差相位延迟器从源头杜绝了这些不良影响，且使用调整方便，大大降低了光路调整及器件装配工艺的难度，提高了光学元器件耦合、光通 信性能和光路的稳定性。
附图说明
图1为本申请一种可能的实施方式中的嵌入式晶体的结构示意图；
图2为本申请一种可能的实施方式中的嵌入式晶体的高分辨透射电镜测试图；
图3为本申请一种可能的实施方式中的嵌入式晶体的扫描电镜测试图；
图4为本申请一种可能的实施方式中的消色差相位延迟器的有效折射率测试图；
图5为本申请一种可能的实施方式中的消色差相位延迟器的有效带隙测试图；
图6a为本申请一种可能的实施方式中的当线偏振光振动方向相对晶体面的夹角为φ°时530nm～800nm的宽波段被消色差相位延迟器调控后的效果；
图6b为本申请一种可能的实施方式中的当线偏振光振动方向相对晶体面的夹角为
Figure PCTCN2019115696-appb-000003
时530nm～800nm的宽波段被消色差相位延迟器调控后的效果；
图6c为本申请一种可能的实施方式中的当线偏振光振动方向相对晶体面的夹角为
Figure PCTCN2019115696-appb-000004
时530nm～800nm的宽波段被消色差相位延迟器调控后的效果。
具体实施方式
以下将结合附图及实施例来详细说明本发明的实施方式，借此对本发明如何应用技术手段来解决技术问题，并达成技术效果的实现过程能充分理解并据以实施。需要说明的是，只要不构成冲突，本发明中的各个实施例以及各实施例中的各个特征可以相互结合，所形成的技术方案均在本发明的保护范围之内。
同时，在以下说明中，出于解释的目的而阐述了许多具体细节，以提供对本发明实施例的彻底理解。然而，对本领域的技术人员来说显而易见的是，本发明可以不用这里的具体细节或者所描述的特定方式来实施。
本申请中，结构表征所采用JEOL-JEM 2100F Transmission Electron Microscopy operating at an acceleration voltage of 200kV仪器；
形貌表征采用EOS 500D Cannon camera仪器；
折射率测试采用ES01-M fast spectroscopic spectral ellipsometer(Ellitop Scientific Co.,Ltd.,China)仪器；
带隙测试采用Persee TU-1901 UV/Vis spectrophotometer仪器。
为解决现有技术中的宽波段消色差相位延迟器存在延迟精度较低、消色差度低、结构复杂、操作比较麻烦等缺点。首先，本发明提供了一种嵌入式晶体。
其中，晶体的结构为“纳米晶嵌入主基质晶体”；纳米晶的尺寸为1nm～20nm并且在主基质晶体的一个晶面内分布；主基质晶体为折射率小于2、带隙大于2.5eV的透明单晶；并且对于400nm～3000nm波长的光，主基质晶体与纳米晶的折射率差的范围为0.15～2.00。其中，消色差相位延迟器是厚度为0.1cm～0.4cm的晶体片。
图1的a、b、c分别为根据本发明一种可能实现方式中的沿x、y和z方向的纳米晶嵌入主基质晶体结构的示意图。如图1所示，图中内部颜色较暗的部分为嵌入的钙钛矿型纳米晶，外部颜色较浅的部分为钙钛矿型主基质晶体，其中图1a中的外部颜色较浅的部分中的类似圆圈属于主基质晶体结构中的孤立的{B 2X 2 6} 4-八面体，其他灰色的原子表示A 2，内部深色部分表示纳米晶结构中的角共享的{B 1X 1 6} 4-八面体，大圆球与大圆球之间的小圆球表示A 1。
在本发明可能的实施方式中，主基质晶体为宽带隙透明单晶，其折射率小于2(以波长λ＝532nm为准)。其中，宽带隙透明单晶为带隙大于2.5eV的单晶，当单晶的带隙大于2.5eV时，此时单晶会透明或偏绿、偏蓝的透明。
在本发明可能的实施方式中，纳米晶的材料与主基质晶体的材料不同，并且纳米晶在主基质晶体的一个晶面内分布。纳米晶为尺寸约1nm～20nm的纳米颗粒，其折射率不等于主基质晶体的折射率，即纳米晶的折射率大于或小于主基质晶体的折射率。优选地，在本发明可能的实施方式中，对于400nm～3000nm波长的光，主基质晶体与纳米晶的折射率差的范围为0.15～2.00。
需要说明的是，对于400nm～3000nm波段任意一波长，宽带隙透明单晶与纳米晶的折射率差的范围均为0.15～2.00。
在本发明可能的实施方式中，主基质晶体的材料是从包括以下项的组中选择的任一项：
结构通式为A 4BX 6的材料，其中A为Na、K、Rb和Cs中的一个或两个，B为Pb、Sn、Ge、Mn、Mg、Mo、Cu、Zn、Cd、Ca或Sr；X为F、Cl、Br和I中的一个或两个；
结构通式为R 4BX 6的材料，其中R为CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +和C 6H 5(CH 2) nNH 2中的一个或两个，其中n＝0至10，“＝”表示双键，B为Pb、Sn、Ge、Mn、Mg、Mo、Cu、Zn、Cd、Ca或Sr，X为F、Cl、Br和I中的一个或两个；
结构通式为AX的材料，其中A为Na、K、Rb或Cs；X为F、Cl、Br或I；
结构通式为RX的材料，其中R为CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +或C 6H 5(CH 2) nNH 2，其中n＝0至10，“＝”表示双键；X为F、Cl、Br或I；
柠檬酸三钠Na 3C 6H 5O 7·2H 2O；
石英；以及云母。
在本发明可能的实施方式中，纳米晶的材料是从包括以下项的组中选择的任一项：
结构通式为ABX 3的材料，其中A为K、Rb或Cs，B为Pb、Sn、Ge、Mn、Mo、Cu或Sr，X为F、Cl、Br和I中的一个或两个；
结构通式为RBX 3的材料，其中R为CH 3(CH 2) nNH 3或NH＝CHNH 3 +，其中n＝0至3，“＝”表示双键，B为Pb、Sn、Ge、Mn、 Mo、Cu或Sr，X为F、Cl、Br和I中的一个或两个；
碳点；以及MgF。
需要说明的是，在本发明可能的实施方式中，以结构通式为A 4BX 6的材料为例，其中，当A为Na、K、Rb和Cs中的两个时，指的是结构通式中的A 4是由Na、K、Rb和Cs中的任意两种元素组成，只要这两种元素的化学式数字下标相加等于A 4的数字下标即可。例如A 4可以是Na 2K 2、Rb 2Cs 2或Rb 3K，分别对应的结构通式为Na 2K 2BX 6、Rb 2Cs 2BX 6或Rb 3KBX 6。此外，当R和X为多个元素中的两个时，与上述A的情况相同，在此不再赘述。
优选地，晶体主基质的折射率小于1.8(以波长λ＝532nm为准)。
在本发明可能的实施方式中，具有“纳米晶嵌入主基质晶体”结构的晶体是由以下方式形成的：纳米晶通过原位嵌入主基质晶体。即通过原位嵌入的方式，使得长晶体的时候会原位形成主基质晶体包含纳米晶的结构。
在本发明另一可能的实施方式中，具有“纳米晶嵌入主基质晶体”结构的晶体还可以是由以下方式形成的：通过在生长出主基质晶体后以后期调控的方式形成纳米晶而制成。过程为：通过高能激光、X-射线或电子束等进行辐照，或者通过高温加热、加压或超声波振动等，对主基质晶体施加能量，使得在主基质晶体的结构中形成纳米晶。
需要说明的是，也可以由其他方式获得“纳米晶嵌入主基质晶体”结构的晶体，本发明不限于此。
在本发明可能的实施方式中，利用晶体制成的消色差相位光学延迟器是厚度为0.1cm～0.4cm的晶体片。
优选地，晶体经过切片打磨抛光后被制成厚度0.1cm～0.4cm的晶体片。只需一片该晶体片就能够实现消色差四分之一波片的全部性能。其中，切片是指使用刀片、激光等切割成片。打磨抛光是指使用抛光粉或抛光膏在砂纸、尼龙布、羊毛布、纤维、植绒羊毛或丝绸上将晶体片打磨抛光至表面呈镜面光滑。
为使得透光效果最佳，优选地，利用晶体制成的消色差相位延 迟器是直径0.5cm～3cm、厚度0.1cm～0.4cm的晶体圆片。
在本发明可能的实施方式中，利用晶体制成的消色差相位延迟器的适用波长段为400nm～3000nm。亦即，对于400nm～3000nm波段任意波长的光，消色差相位延迟器都可以实现消色差四分之一波片的全部性能。即，可以将入射线偏振光的相位延迟
Figure PCTCN2019115696-appb-000005
或将本来具有
Figure PCTCN2019115696-appb-000006
相位差的圆偏振光调控为相位差为π或其他整数倍的线偏振光，或将线偏振光调控成圆偏振光，可实现线偏振光和圆偏振光的相互转换。
相应地，本发明可能的实施方式还提供一种利用晶体制作消色差相位延迟器的方法，晶体的结构为纳米晶嵌入主基质晶体，纳米晶的尺寸为1nm～20nm并且在主基质晶体的一个晶面内分布，主基质晶体为折射率小于2、带隙大于2.5eV的透明单晶，并且对于400nm～3000nm波长的光，主基质晶体与纳米晶的折射率差的范围为0.15～2.00，
其中，该方法包括：
将晶体制成直径为0.5cm～3cm、厚度为0.1cm～0.4cm的圆片。
在本发明可能的实施方式中，通过将纳米晶原位嵌入主基质晶体而制成晶体。
在本发明可能的实施方式中，通过在生长出主基质晶体后以后期调控的方式形成纳米晶而制成晶体。
在本发明可能的实施方式中，后期调控的方式包括：通过高能激光、X-射线或电子束进行辐照，或者通过高温加热、加压或超声波振动，对主基质晶体施加能量，使得在主基质晶体的结构中形成纳米晶。
综上所述，本发明提供了一种利用晶体制成的消色差相位延迟器和制作方法，本发明从晶体材料的结构设计出发，通过在单晶中嵌入纳米晶体形成了一种新的晶体，最终只用单片该晶体便实现了 消色差四分之一波片的全部性能，可以将可见光至红外(400nm～3000nm)超宽波段的光相位延迟
Figure PCTCN2019115696-appb-000007
也可将此波段相位差
Figure PCTCN2019115696-appb-000008
的光调控成π或其整数倍，避免了现有宽波段消色差波片需要粘连多个和多种晶体等繁琐的工艺及光学设计的过程。
现有的消色差相位延迟器的设计过程往往影响着适用波段的宽窄、延迟精度等相位延迟器的技术要求，而本发明提供的消色差相位延迟器从源头杜绝了这些不良影响，且使用调整方便，大大降低了光路调整及器件装配工艺的难度，提高了光学元器件耦合、光通信性能和光路的稳定性。
方法一
实施例1 1#嵌入式晶体的制备(以原位嵌入的方式制备)
制备Cs 4PbCl 6，选择1mmol的CsCl和5mmol的PbCl 2，在富Cl -的40mL HCl中溶解，加热至80℃溶解后，自然冷却降至室温(25℃)，即可得到CsPbCl 3纳米晶嵌入Cs 4PbCl 6主基质晶体的嵌入式晶体，记作1#嵌入式晶体。
实施例2 2#嵌入式晶体的制备(以原位嵌入的方式制备)
制备碳点嵌入柠檬酸三钠主基质的晶体时，将1g柠檬酸三钠和2g尿素溶解在10ml N,N-二甲基甲酰胺中。然后将溶液转移到高压釜中(本申请中，高压釜的压力可以为2MPa～32MPa，具体本实施例中为5Mpa)，并在160℃加热4h，之后，将反应器自然冷却至室温(30℃)，得到碳点嵌入柠檬酸三钠主基质晶体的嵌入式晶体，记作2#嵌入式晶体。
方法二
实施例3 3#嵌入式晶体的制备(以后期调控的方式制备-高温退火)
制备Cs 4PbI 6，选择1mmol的CsI和8mmol的PbI 2，在40mL N,N二甲基甲酰胺中溶解，加热至140℃溶解后缓慢降至室温，得到Cs 4PbCl 6主基质单晶。之后在200℃退火5小时，得到CsPbI 3纳米晶嵌入Cs 4PbI 6主基质晶体的嵌入式晶体，记作3#嵌入式晶体。
实施例4 4#嵌入式晶体的制备(以后期调控的方式制备-高能激光)
制备(NH＝CHNH 3) 4SnBr 6：选择1mol的NH＝CHNH 3Br和3mol的SnBr 2，氮气气氛下在10mL N,N二甲基甲酰胺中溶解，加热至140℃溶解后缓慢降至室温，得到(NH＝CHNH 3) 4SnBr 6主基质单晶。之后使用633nm氦氖激光器辐照4小时，得到NH＝CHNH 3SnBr 3纳米晶嵌入(NH＝CHNH 3) 4SnBr 6主基质晶体的嵌入式晶体，记作4#嵌入式晶体。
实施例5 5#嵌入式晶体的制备(以后期调控的方式制备-声波振动)
制备(C(NH 2) 3) 4CuBr 6：选择2mol的C(NH 2) 3Br和10mol的CuBr 2，在25mL N,N二甲基甲酰胺和25mL HBr中溶解，加热至90℃溶解后缓慢降至室温，得到(C(NH 2) 3) 4CuBr 6主基质单晶。之后放置在超声波或微波振动场中7小时，得到C(NH 2) 3CuBr 3纳米晶嵌入(C(NH 2) 3) 4CuBr 6主基质晶体的嵌入式晶体，记作5#嵌入式晶体。
实施例6 6#嵌入式晶体的制备(以后期调控的方式制备-高温退火)
制备Cs 4PbI 6主基质嵌入CH 3NH 3PbBr 3纳米晶。选择1mmol的CsI和8mmol的PbI 2，在40mL N,N二甲基甲酰胺中溶解，加热至140℃溶解配制成主基质溶液，并保持该温度放置24小时。
再取0.1mmol CH 3NH 3PbBr 3粉末加入到溶解好的主基质溶液中，加热140℃后缓慢降至室温，得到Cs 4PbI 6主基质单晶。之后在120℃退火5小时，得到CH 3NH 3PbBr 3纳米晶嵌入Cs 4PbI 6主基质晶体的嵌 入式晶体，记作6#嵌入式晶体。
方法三
实施例7 7#嵌入式晶体的制备
制备MgF 2纳米晶嵌入氯化钠主基质的晶体时，将1mmol氟化镁，100μL油酸溶解在硝酸里，滴入快速搅拌的环庚烷中，持续搅拌1分钟后离心取下沉淀，标记为沉淀1。
取80g氯化钠、100ml蒸馏水放入250mL锥形瓶中加热至50℃，配制饱和溶液。取沉淀1加入到氯化钠饱和溶液中，将锥形瓶自然冷却至室温，得到7#嵌入式晶体。
实施例8晶体结构的表征
分别对实施例1至实施例7中的嵌入式晶体进行透射电镜测试，测试结果显示，纳米晶嵌入主基质晶体中，形成嵌入式的结构。
以实施例1中的样品为典型代表，对Cs 4PbCl 6中的CsPbCl 3纳米晶进行透射电镜测试，高分辨透射电镜测试结果如图2所示，通过对图2的晶格间距及晶系对比确认图2中表明纳米晶为CsPbCl 3，主基质晶体为Cs 4PbCl 6，纳米晶CsPbCl 3嵌入主基质晶体Cs 4PbCl 6中形成嵌入式的结构。
实施例9晶体的形貌表征
分别对实施例1至实施例7中的嵌入式晶体进行扫描电镜测试，测试结果显示，纳米晶的尺寸小于20nm。
以实施例5中的嵌入式晶体为典型代表进行扫描电镜测试，测试结果如图3所示，图3示，纳米晶的尺寸小于20nm，其中，图中的黑色的小圆点为纳米晶；灰色的大圆点为主基质。
实施例10消色差相位延迟器的制备
将实施例1中的嵌入式晶体制备(切割)成直径0.5～3cm，厚 度0.1～0.4cm的圆片，打磨抛光晶体表面粗糙度小于1nm，记作1#消色差相位延迟器。
实施例2至7中的嵌入式晶体制备消色差相位延迟器的方法同上，此处不在赘述，分别记作2#～7#消色差相位延迟器。
实施例11消色差相位延迟器的性能测试
对该1#消色差相位延迟器中主基质晶体Cs 4PbCl 6和纳米晶CsPbCl 3的折射率在可见光区宽波段的氙灯照射进行测试，测试结果如图4所示，图4表明，晶体在550-800nm波段其有效折射率在1.749-1.735之间。
4#消色差相位延迟器中主基质晶体实例4的带隙利用吸收性质进行测试，测试结果如图5所示，图5表明，晶体有效带隙为2.64eV。
实施例12 1#消色差相位延迟器的调控测试
图6a、图6b和图6c分别为当线偏振光振动方向相对晶体面的夹角为
Figure PCTCN2019115696-appb-000009
和
Figure PCTCN2019115696-appb-000010
时530nm～800nm的宽波段光被1#消色差相位延迟器调控后的效果图，其中
Figure PCTCN2019115696-appb-000011
可以是任意角度。如图6a所示，当线偏振光振动方向相对晶体面的夹角为
Figure PCTCN2019115696-appb-000012
时，入射线偏振光被消色差相位延迟器调控为圆偏振光(出射光)，纵轴则说明在530nm～800nm波段内都有这个效应。如图6b所示，当线偏振光振动方向相对晶体面的夹角为
Figure PCTCN2019115696-appb-000013
时，此时
Figure PCTCN2019115696-appb-000014
正好为光直接透过角度，即对于530nm～800nm波段的线偏振光，入射到消色差相位延迟器后出射光还是线偏振光。如图6c所示，当线偏振光振动方向相对晶体面的夹角为
Figure PCTCN2019115696-appb-000015
时，其过程与图6a的过程相同，在此不再赘述。
应该理解的是，本发明所公开的实施例不限于这里所公开的特定处理步骤或材料，而应当延伸到相关领域的普通技术人员所理解 的这些特征的等同替代。还应当理解的是，在此使用的术语仅用于描述特定实施例的目的，而并不意味着限制。
说明书中提到的“实施例”意指结合实施例描述的特定特征、或特性包括在本发明的至少一个实施例中。因此，说明书通篇各个地方出现的短语“实施例”并不一定均指同一个实施例。
此外，所描述的特征或特性可以任何其他合适的方式结合到一个或多个实施例中。在上面的描述中，提供一些具体的细节，例如厚度、数量等，以提供对本发明的实施例的全面理解。然而，相关领域的技术人员将明白，本发明无需上述一个或多个具体的细节便可实现，或者也可采用其它方法、组件、材料等实现。
虽然上述示例用于说明本发明在一个或多个应用中的原理，但对于本领域的技术人员来说，在不背离本发明的原理和思想的情况下，明显可以在形式上、用法及实施的细节上作各种修改而不用付出创造性劳动。因此，本发明由所附的权利要求书来限定。

Claims (17)

  1. 一种嵌入式晶体，其特征在于，所述嵌入式晶体包括纳米晶和主基质晶体，所述纳米晶嵌入所述主基质晶体且分布于所述主基质晶体的某一晶面。
  2. 根据权利要求1所述的嵌入式晶体，其特征在于，所述纳米晶的尺寸为1nm～20nm。
  3. 根据权利要求1所述的嵌入式晶体，其特征在于，所述纳米晶选自具有钙钛矿结构的晶体Ⅰ、碳点、MgF 2中的任一种。
  4. 根据权利要求3所述的嵌入式晶体，其特征在于，所述具有钙钛矿晶体结构的晶体Ⅰ选自具有式Ⅰ所示化学式的化合物中的任一种；
    A 1B 1X 1 3  式Ⅰ
    其中，A 1选自K +、Rb +、Cs +、CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +中的至少一种，n为整数，n的取值范围为0≤n≤3；
    B 1选自Pb 2+、Sn 2+、Ge 2+、Mn 2+、Mo 2+、Cu 2+、Sr 2+中的至少一种；
    X 1选自F -、Cl -、Br -和I -中的至少一种。
  5. 根据权利要求1所述的嵌入式晶体，其特征在于，所述主基质晶体选自具有钙钛矿结构的晶体Ⅱ、具有氯化钠结构的晶体、柠檬酸三钠、石英、云母中的至少一种。
  6. 根据权利要求5所述的嵌入式晶体，其特征在于，所述具有钙钛矿结构的晶体Ⅱ选自具有式Ⅱ所示化学式的化合物中的任一种；
    A 2 4B 2X 2 6  式Ⅱ
    其中，A 2选自Na +、K +、Rb +、Cs +、CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +、C 6H 5(CH 2) nNH 2 +中的至少一种，n为整数，n的取值范围为0≤n≤10；
    B 2选自Pb 2+、Sn 2+、Ge 2+、Mn 2+、Mg 2+、Mo 2+、Cu 2+、Zn 2+、Cd 2+、Ca 2+、Sr 2+中的至少一种；
    X 2选自F -、Cl -、Br -和I -中的至少一种。
  7. 根据权利要求5所述的嵌入式晶体，其特征在于，所述具有氯化钠结构的晶体选自具有式Ⅲ所示化学式的化合物中的任一种；
    A 3X 3  式Ⅲ
    其中，A 3选自Na +、K +、Rb +、Cs +、CH 3(CH 2) nNH 3 +、NH＝CHNH 3 +、C(NH 2) 3 +、C 6H 5(CH 2) nNH 2 +中的至少一种，n为整数，n的取值范围为0≤n≤10；
    X 3选自F -、Cl -、Br -和I -中的至少一种。
  8. 权利要求1至7任一项所述嵌入式晶体的制备方法，其特征在于，采用方法一、方法二或者方法三制备得到；
    所述方法一至少包括以下步骤：将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中，原位生长形成所述嵌入式晶体；
    所述方法二至少包括以下步骤：将含有纳米晶源和主基质晶体源的混合物，加热，降温，在降温过程中形成主基质晶体，之后经过外界调控，在所述主基质晶体中形成纳米晶，得到所述嵌入式晶体；
    其中，所述外界调控包括退火处理、激光辐照、微波振动、声波振动、加压处理中的任一种；
    所述方案三至少包括以下步骤：将纳米晶加入含有主基质晶体的溶液中，降温，所述纳米晶嵌入所述主基质晶体中，得到所述嵌入式晶体。
  9. 根据权利要求8所述的制备方法，其特征在于，在所述方法一中，将所述含有纳米晶源和主基质晶体源的混合物加热至80～160℃，降温至20～30℃，得到所述嵌入式晶体。
  10. 根据权利要求8所述的制备方法，其特征在于，所述方法二包括：将含有纳米晶源和主基质晶体源的混合物加热至140～160℃，降温，得到主基质晶体，之后进行退火处理，得到嵌入式晶体；
    所述退火处理的条件为：退火温度120～220℃；退火时间5～6h。
  11. 根据权利要求8所述的制备方法，其特征在于，所述方法 二包括：将含有纳米晶源和主基质晶体源的混合物加热至140～160℃，降温，得到主基质晶体，之后进行激光辐照处理，得到所述嵌入式晶体；
    所述激光辐照处理的条件为：激光波长600～1000nm；辐照时间4～6h。
  12. 根据权利要求8所述的制备方法，其特征在于，所述方法二包括：将含有纳米晶源和主基质晶体源的混合物加热至140～160℃，降温，得到主基质晶体，之后放置于微波振动场或声波振动场中，处理7～10h，得到所述嵌入式晶体。
  13. 一种消色差相位延迟器，其特征在于，所述消色差相位延迟器包括权利要求1至7中任一项所述的嵌入式晶体和/或权利要求8至12中任一项所述的制备方法得到的嵌入式晶体中的任一种。
  14. 根据权利要求13所述的消色差相位延迟器，其特征在于，在所述嵌入式晶体中，所述主基质晶体为透明晶体；
    所述主基质晶体的折射率小于2；
    所述主基质晶体的带隙大于2.5eV。
  15. 根据权利要求14所述的消色差相位延迟器，其特征在于，所述主基质晶体的折射率小于1.8。
  16. 根据权利要求13所述的消色差相位延迟器，其特征在于，所述嵌入式晶体为直径0.5～100cm且厚度0.01～1cm的圆片。
  17. 根据权利要求13所述的消色差相位延迟器，其特征在于，在波长为400～3000nm的光照射下，所述主基质晶体与纳米晶的折射率差Δn的绝对值的取值范围为0.15≤∣Δn∣≤2.00。
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