WO2012121111A1 - Eu(II)化合物及び金属を含有する複合ナノ結晶及び複合薄膜 - Google Patents
Eu(II)化合物及び金属を含有する複合ナノ結晶及び複合薄膜 Download PDFInfo
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Definitions
- Various aspects and embodiments of the present invention relate to composite nanocrystals and composite thin films containing an Eu (II) compound and a metal.
- Bi-substituted garnets are known as materials for ultra-compact optical isolators corresponding to optical communication wavelength bands (1.3 ⁇ m, 1.55 ⁇ m) (see, for example, Patent Document 1).
- Patent Document 1 by combining nanoparticles such as Au, Al, and Ag inside a Bi-substituted garnet thin film, the electric polarization induced in the metal nanoparticles is increased by the surface plasmon resonance of the metal nanoparticles. This increases the magneto-optic effect of the Bi-substituted garnet.
- Eu (II) compounds Europium chalcogenide
- EuO show strong light absorption and emission due to fd transition in Eu (II) having seven unpaired f electrons, and ferromagnetic properties. Therefore, its magneto-optical characteristics are attracting attention and are expected to be used as optical isolator materials. Among these characteristics, the Faraday effect in which the polarization plane of light is rotated by applying a magnetic field has attracted attention (see, for example, Patent Documents 2 and 3).
- Patent Documents 2 and 3 suggest that EuO nanocrystals exhibit magneto-optical properties at room temperature due to the quantum size effect.
- An object of this invention is to provide the material which improved the magneto-optical characteristic.
- the inventors of the present invention have placed an Eu (II) compound and a metal that forms a localized electric field on the surface by light irradiation, thereby providing an Eu (II) compound. It has been found that the Faraday effect increases significantly.
- the composite nanocrystal according to one aspect of the present invention is formed by combining metal nanoparticles with Eu (II) compound nanoparticles.
- the surface plasmon of the metal nanoparticles can be used while exhibiting the quantum size effect of the Eu (II) compound nanoparticles. For this reason, it is possible to improve the magneto-optical characteristics.
- the Eu (II) compound nanoparticles may be formed of a material selected from EuO, EuS, EuSe, or EuTe.
- the metal nanoparticles may be formed of a metal material selected from Ag, Au, Pt and Cu, a combination of the metal materials, or two or more kinds of alloys selected from Ag, Au, Pt and Cu. Also good.
- the crystalline Eu (II) compound nanoparticles and the crystalline metal nano particles are formed by a compound having two or more of the same or different thiol group, hydroxyl group, carboxyl group, sulfonic acid group, cyano group, amino group or pyridyl group. The particles may be combined.
- the composite thin film according to another aspect of the present invention is formed by combining metal nanoparticles with Eu (II) compound nanoparticles.
- the composite thin film thus configured has the same effects as the composite nanocrystal.
- the magneto-optical material according to still another aspect of the present invention is formed using the above-described composite nanocrystal or composite thin film. Since Eu (II) compound nanoparticles have a characteristic that the magnetic susceptibility changes by light irradiation, for example, the above-mentioned composite nanocrystal or composite thin film is adopted as a Faraday rotator, and the polarization plane is rotated in response to light. It is possible to provide an optical device such as an optical isolator that can not be realized by conventional techniques.
- the inorganic glass or polymer thin film according to still another aspect of the present invention is formed using the above composite nanocrystal or composite thin film.
- a magneto-optical material such as a novel optical isolator and a recording medium can be provided.
- an optical isolator includes a Faraday rotator formed using the above-described composite nanocrystal, composite thin film, magneto-optical material, or inorganic glass thin film. By comprising in this way, the polarization plane rotation effect similar to an optical isolator provided with the Faraday rotator made from a garnet crystal can be acquired.
- the method for producing a composite nanocrystal according to still another aspect of the present invention includes a step of synthesizing crystalline Eu (II) compound nanoparticles by thermally reducing a complex containing Eu (III), A step of synthesizing crystalline metal nanoparticles by thermally reducing a metal-containing complex; and the same or different thiol group, hydroxyl group, carboxyl group, and the Eu (II) compound nanoparticles and the metal nanoparticles, And a step of synthesizing a composite nanocrystal by bonding with a compound having two or more sulfonic acid groups, cyano groups, amino groups or pyridyl groups.
- a composite nanocrystal can be synthesized by bonding with a compound having two or more groups, amino groups or pyridyl groups.
- the method for producing a composite nanocrystal according to still another aspect of the present invention includes a step of mixing a complex containing Eu (III) and a complex containing a metal, and a thermal reduction reaction of the mixed complex. Synthesizing the composite nanocrystal.
- a composite nanocrystal can be synthesized by mixing a complex containing Eu (III) and a complex containing a metal and simultaneously performing a thermal reduction reaction.
- a method for producing a composite thin film according to still another aspect of the present invention is a method for producing a composite thin film electrochemically, wherein a complex containing Eu (III) and a complex containing a metal are used as a solvent. And forming a composite thin film composed of Eu (II) compound nanoparticles and metal nanoparticles on the transparent electrode by applying a voltage by inserting the transparent electrode into the solvent and applying a voltage. And comprising the steps of:
- the composite thin film can be formed by electrochemical action.
- a method for producing a composite thin film according to still another aspect of the present invention is a method for producing a composite thin film electrochemically, and comprises an Eu dispersion step of dispersing a complex containing Eu (III) in a solvent.
- a thin film comprising a Eu (II) compound or a metal by dispersing a metal-containing complex in a solvent and using a transparent electrode as a working electrode, inserting the transparent electrode into the solvent and applying a voltage Forming a thin film on the transparent electrode, and performing the Eu dispersion step, the thin film formation step, the metal dispersion step and the thin film formation step in this order, or the metal dispersion step and the thin film formation step.
- the Eu dispersion step and the thin film formation step are executed in this order.
- the Faraday effect of the Eu (II) compound can be greatly increased by arranging the Eu (II) compound and a metal that forms a localized electric field on the surface by light irradiation in close proximity.
- (A) is an SEM image
- (B) is a mapping result of Eu
- (C) is a mapping result of S
- (D) is a mapping result of Si.
- It is a time change of the current value of the EuS thin film (applied voltage -1.2 V). It is a measurement result of the light absorption spectrum in an Example and a comparative example.
- It is a schematic block diagram of the conventional optical isolator. It is a schematic block diagram of the optical isolator which has the structure which rotates the polarization plane of a Faraday rotator with a laser beam. It is a Berde constant spectrum diagram of a PMMA film containing EuS crystals and a PMMA film containing composite nanocrystals.
- the composite nanocrystal according to the embodiment of the present invention is a composite nanocrystal in which crystalline Eu (II) compound nanoparticles and crystalline metal nanoparticles are combined.
- the composite nanocrystal means a nano-sized composite crystal.
- the size of the Eu (II) compound nanoparticles is, for example, an average particle diameter of about 5 nm to 100 nm.
- Eu (II) compound nanoparticles for example, EuO, EuS, EuSe, or EuTe europium chalcogenide is used.
- the size of the metal nanoparticles for example, the average particle size is about 5 nm to 100 nm.
- the metal nanoparticle material may be any metal material that forms a localized electric field on the surface by light irradiation, and for example, Ag, Au, Pt, Cu, or a combination thereof is used. Alternatively, two or more kinds of alloys selected from Ag, Au, Pt and Cu may be used.
- the composite nanocrystal is configured such that the crystalline Eu (II) compound nanoparticles and the crystalline metal nanoparticles are joined at their interfaces.
- Any interface joining means may be used, for example, Eu (II) compound nanoparticles and metal nanoparticles may be crystallized and synthesized at the same time, and the particles may be bonded in close contact with each other.
- Eu (II) compound nanoparticles and crystalline metal nanoparticles may be independently prepared and bonded using a bonding material.
- the bonding material for example, compounds having two or more thiol groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, cyano groups, amino groups, or pyridyl groups, which are the same or different, are used.
- Examples of the compound having two or more thiol groups include ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,2-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 3,6-dioxaoctane-1,8-dithiol, 2,2'-oxydiethane Thiol, 2,3-dimercapto-1-propanol, dithioerythritol, dithiothreitol, 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithiol, 4-chloro-1,3-benzenedithiol 4-methyl-1,2-benzenedithiol, 4,5-di
- Examples of the compound having a thiol group and a hydroxyl group include 1-mercaptoethanol, 2-mercaptoethanol, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1.
- 2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like are used.
- Examples of the compound having a thiol group and a carboxyl group include thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptopropionic acid, and the like.
- Examples of the compound having a thiol group and a sulfonic acid group include 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 2-mercaptobenzenesulfonic acid, 3-mercaptobenzenesulfonic acid, 4-mercaptobenzenesulfonic acid, and the like. Is used.
- Examples of the compound having a thiol group and a cyano group include 2-cyanobenzenethiol.
- Examples of the compound having a thiol group and an amino group include aminothiophenol and aminotriazole thiol.
- Examples of the compound having a thiol group and a pyridyl group include pyridine thiol.
- Eu (III) carbamide complex [Eu (PPh 4 ) (S 2 CNEt 2 )], which is a raw material for synthesis of EuS nanocrystals
- Au complex [Au (PPh 3 ), which is a raw material for synthesis of Au nanocrystals Cl] is prepared.
- the Eu (III) carbamide complex and Au complex are dispersed in a solvent.
- a solvent for example, oleylamine is used as the solvent.
- the oleylamine is, for example, about 4.5 g.
- the resulting solution is then heated under a nitrogen atmosphere.
- the heating condition is, for example, 140 ° C. for 5 minutes. Thereby, a solution colored black is obtained.
- heating is performed at a higher temperature in a nitrogen atmosphere.
- the heating condition is, for example, 180 ° C. for 10 minutes. Thereby, a solution having a deep purple color is obtained.
- the resulting solution is then centrifuged.
- the conditions are, for example, room temperature, 7000 rpm, 5 minutes, and oleylamine is used as a solvent.
- Method 2 for producing composite nanocrystal A second method for producing a composite nanocrystal according to the embodiment will be described with reference to FIGS. Similar to the first manufacturing method, the case where EuS is used as the Eu (II) compound and Au is used as the metal will be described.
- Eu (III) carbamide complex [Eu (PPh 4 ) (S 2 CNEt 2 )] which is a raw material for synthesizing EuS nanocrystals, and a raw material for synthesizing Au nanocrystals Au complex: [Au (PPh 3 ) Cl] is prepared.
- EuS nanocrystal particles and Au nanocrystal particles are respectively synthesized.
- a solution in which Eu (III) carbamide complex is dispersed in a solvent is prepared and heated.
- oleylamine is used as the solvent.
- the heating condition is, for example, 140 ° C. for 10 minutes.
- the resulting solution is then heated under a nitrogen atmosphere.
- the heating condition is, for example, 300 ° C. for 6 hours.
- FIG. 2 shows the structure evaluation of EuS nanocrystal particles obtained in the above manufacturing process.
- FIG. 2 is an X-ray diffraction (XRD) pattern of EuS. As shown in FIG.
- EuS nanocrystal particles may be produced by a method using a reduction reaction of Eu (III) using light, as described in JP-A-2001-354417, for example.
- Eu (III) europium nitrate and urea are dissolved in methanol and irradiated with ultraviolet light to produce EuO crystals or EuS crystals.
- a solution in which an Au complex is dispersed in a solvent is prepared and heated.
- the heating condition is, for example, 140 ° C. for 10 minutes.
- the resulting solution is then heated under a nitrogen atmosphere.
- the heating condition is, for example, 300 ° C. for 6 hours.
- Au nanocrystal particles are obtained by the thermal reduction reaction.
- EuS nanocrystal particles and Au nanocrystal particles are joined.
- 1,6-hexanedithiol is used as the bonding material.
- EuS nanocrystal particles and Au nanocrystal particles are connected, and EuS-Au composite nanocrystal particles are obtained.
- the structural evaluation of the EuS-Au composite nanocrystal particles obtained in the above manufacturing process is shown below.
- the structure was evaluated by TEM and absorption spectrum measurement.
- 5 and 6 are TEM images. As shown in FIGS. 5 and 6, it was confirmed that Au having a particle size of about 10 nm was bonded to EuS having a particle size of about 15 nm.
- FIG. 7 is an absorption spectrum at a wavelength of 400 nm to 900 nm. As shown in FIG. 7, the 4f-5d band and the plasmon absorption band of EuS-Au composite nanocrystal particles were confirmed.
- 8A shows absorption spectra of EuS nanocrystals and Au nanocrystals, and FIG.
- the composite thin film according to the embodiment of the present invention is a composite thin film composed of crystalline Eu (II) compound nanoparticles and crystalline metal nanoparticles.
- the film thickness is, for example, about 5 nm to 100 ⁇ m.
- the size of the Eu (II) compound nanoparticles is, for example, an average particle diameter of about 5 nm to 100 nm.
- As a material for Eu (II) compound nanoparticles for example, EuO, EuS, EuSe, or EuTe europium chalcogenide is used.
- the metal nanoparticles have an average particle size of about 5 nm to 100 nm, for example.
- any metal that forms a localized electric field on the surface by light irradiation may be used.
- Ag, Au, Pt, Cu, or a combination thereof is used.
- two or more kinds of alloys selected from Ag, Au, Pt and Cu may be used.
- the composite thin film is configured such that the crystalline Eu (II) compound nanoparticles and the crystalline metal nanoparticles are bonded at their interfaces.
- Any interface joining means may be used, for example, Eu (II) compound nanoparticles and metal nanoparticles may be crystallized and deposited simultaneously, or a thin film made of Eu (II) compound nanoparticles.
- a thin film made of metal nanoparticles may be laminated thereon, or a thin film made of Eu (II) compound nanoparticles may be doped with metal nanoparticles.
- Eu (III) carbamide complex [Eu (PPh 4 ) (S 2 CNEt 2 )], which is a raw material for synthesis of EuS nanocrystals
- Au complex [Au (PPh 3 ), which is a raw material for synthesis of Au nanocrystals Cl] is prepared.
- the components of the complex are identified by NMR, IR, elemental analysis and the like.
- the Eu (III) carbamide complex, Au complex and supporting electrolyte are dispersed in a solvent.
- the supporting electrolyte for example, tetraethylammonium hexafluorophosphate is used.
- acetonitrile is used as the solvent. Note that the Eu (III) carbamide complex and Au complex may be dispersed in different solvents.
- a transparent electrode is used as the working electrode WE for thin-film electrochemical synthesis, and the transparent electrode WE, the reference electrode RE, and the counter electrode CE are inserted into a solvent and degassed with Ar. Apply.
- the transparent electrode for example, tin-doped indium oxide (ITO: Indium Tin Oxide) is used, and platinum (Pt) is used as the reference electrode and the counter electrode.
- an Au thin film made of Au nanoparticles is formed on the EuS thin film by inserting a transparent electrode into a solvent in which the Au complex is dispersed and applying a voltage.
- the formation process of the Au thin film and the EuS thin film may be performed alternately. Thereby, a layered structure of EuS / Au composite thin film is formed.
- 10 and 11 are images of a scanning electron microscope (SEM: Scanning Electron Microscope). As shown in FIG. 10, it was confirmed that a thin film of about 100 ⁇ m was formed on the transparent electrode. Moreover, as shown in FIG. 11, it was confirmed that it is a thin film consisting of nanoparticles. Furthermore, elemental components were evaluated with an energy dispersive X-ray analyzer (EDS: Energy Dispersion Spectroscopy). As a result, it was confirmed that the ratio of Eu and S was 1: 1.
- EDS Energy Dispersion Spectroscopy
- an EuS thin film that is a continuous film and has an appropriate composition ratio can be formed.
- the creation conditions for the EuS thin film are as follows. Solvent: acetonitrile 20ml Supporting electrolyte: tetraethylammonium hexafluorophosphate 0.1 mol / l Sample: Eu (III) dithiocarbamide complex 0.06 mol / l Deaeration with Ar: 15 minutes First, in order to verify whether or not a change from Eu (III) to Eu (II) occurs under the above conditions, the voltage applied to the reference electrode and the counter electrode was changed at 100 mV / s.
- FIG. 13 is an SEM image of the EuS thin film. (A) shows sample no. No.
- sample No. 5 is an SEM image of 5.
- FIG. 13A it was confirmed that when the applied voltage was ⁇ 0.8 V, an island structure was formed instead of a film. This is probably because EuS did not grow sufficiently because current did not flow sufficiently.
- FIGS. 13C to 13E it was confirmed that when the applied voltage was ⁇ 1.4 V or more, a part of the film was peeled off to form a discontinuous film. It can be considered that EuS grew too much depending on the location and became a lump and separated because the current flowed sufficiently.
- Table 1 shows the evaluation results of the ratio of Eu and S. As shown in Table 1, it was confirmed that the ratio of Eu to S was about 1: 1 when the applied voltage was in the range of 0.8V to 1.4V. Thus, it was confirmed that a suitable EuS thin film grows when the applied voltage is -1.2V.
- FIG. 2 is an SEM image of 2 EuS thin film.
- (A), (B), (C), and (D) are SEM images with smaller scales, and were observed in detail in units of ⁇ m. As shown in FIG. 14, it was confirmed that a thin film was formed when the applied voltage was -1.2V. Next, sample no. Two components were measured. Sample No. In FIG. 2, measurement is performed by searching for a portion where a part of the continuous film is peeled off, and the glass substrate coated with ITO is also measured. The results are shown in FIG. FIG. 2 is an EDS mapping result of 2.
- (A) is an SEM image
- (B) is a mapping result of Eu
- (C) is a mapping result of S
- (D) is a mapping result of Si.
- (B) to (C) show regions in which white portions are detected as elements. As shown in FIG. 15, it was confirmed that the ratio of Eu and S was 1: 1 in a region other than Si, that is, in a region where a film was formed.
- FIG. 2 is the time change of the current value at the time of creation, and the horizontal axis represents time and the vertical axis represents the current value.
- the current value became constant by applying a constant voltage (-1.2 V) for a long time. For example, after 4 ⁇ 10 3 [s], the current value became a substantially constant value.
- a constant current value indicates a steady state reaction, that is, the same reaction always takes place at the same rate. That is, it was confirmed that when EuS was initially accumulated on the ITO surface and the film thickness increased with time, only the reaction in which EuS accumulated on EuS always occurred at the same rate.
- FIG. 17 shows a sample No. deposited on ITO on a glass substrate.
- 2 is a measurement result of a light absorption spectrum of a glass substrate coated with ITO, and the horizontal axis represents wavelength and the vertical axis represents intensity.
- the light absorption spectrum of the glass substrate coated with ITO is indicated by a dotted line, sample No.
- the light absorption spectrum of 2 is indicated by a solid line.
- FIG. 18 is a schematic configuration diagram of an optical isolator conventionally used. As shown in FIG. 18, the optical isolator has a structure in which a Faraday rotator 10 is placed between a polarizer 11 and an analyzer 12, and the Faraday rotator 10 is sandwiched between permanent magnets 13 that apply a magnetic field. .
- the forward light introduced from the optical fiber 14a is linearly polarized by the polarizer 11, and then the light whose polarization plane is rotated by the Faraday rotator 10 passes through the analyzer 12 to the optical fiber 14b. be introduced.
- the light in the reverse direction is linearly polarized by the analyzer 12 and its plane of polarization is rotated by the Faraday rotator 10, but the rotated light does not coincide with the plane of polarization of the polarizer 11. Cannot pass through the polarizer 11 and the return light is blocked there.
- a Faraday rotator 10 made of garnet crystal has been used.
- the Faraday rotator 10 is formed using the composite nanocrystal or composite thin film containing the Eu (II) compound described above, the same polarization plane rotation effect as the Faraday rotator 10 made of garnet crystal can be obtained. it can. For this reason, it is possible to manufacture an optical isolator for home short-range communication at low cost.
- An optical isolator currently on the market corresponds only to the near infrared region, but an optical isolator in which the Faraday rotator 10 is formed using a composite nanocrystal or a composite thin film containing the above-described Eu (II) compound is used. It corresponds to the ultraviolet and visible regions, and can be used even when multiwavelength communication is to be performed in the near future.
- the composite nanocrystal and composite thin film containing the above-described Eu (II) compound can be applied to an optical switch using the magneto-optical effect.
- it can be employed as a Faraday rotation element of an optical switch.
- the magnetic susceptibility of the composite nanocrystal and composite thin film containing the above-described Eu (II) compound is changed by light irradiation
- a composite nanocrystal and a composite thin film containing an Eu (II) compound in the configuration of FIG. 18 are adopted for the Faraday rotator 10 and a light source such as a laser light source capable of irradiating the Faraday rotator 10 with light is used.
- a light source such as a laser light source capable of irradiating the Faraday rotator 10 with light
- FIG. 1 This optical response isolator has substantially the same structure as a conventional optical isolator, and differs in the following points. That is, a laser light source 15 is provided in place of the permanent magnet, and laser light emitted from the laser light source 15 is incident on the Faraday rotator 10 by the dielectric mirror 16, thereby changing the magnetic susceptibility of the Faraday rotator 10 to change the polarization plane. Is changing.
- the thin film which has a new characteristic can be produced
- a solution containing the above-described composite nanocrystal is made into a colloidal solution by hydrolysis and condensation polymerization reaction, and further, the reaction is promoted to form a gel that loses fluidity.
- An inorganic glass thin film containing nanocrystals can be produced.
- a polymer thin film containing the composite nanocrystal can be generated by dispersing the above-described composite nanocrystal in a dissolved polymer and spraying it on a plate or the like to dry.
- a recording medium such as a magneto-optical disk capable of writing and reading data using the Kerr effect of the Eu (II) compound rotating the polarization direction of the reflected light can be obtained by using the Eu (II) compound described above. It can be produced using a composite nanocrystal containing.
- a magneto-optical disk laser light is applied to a recording surface made of a resin thin film containing composite nanocrystals on the disk surface with a magnetic field that is not strong enough to reverse the magnetization direction in the direction opposite to the magnetization direction.
- the magnetization direction is reversed only in the portion irradiated with the laser beam, and data is written.
- a laser beam weaker than the writing light is applied to the recording surface, and the difference in the Kerr rotation angle of the reflected light is detected using the polar Kerr effect. That is, the recorded signal can be read by detecting the difference in Kerr rotation angle as a change in light intensity using a polarizer.
- Example 2 An acrylic resin (PMMA: Poly (methyl methacrylate)) was dissolved in chloroform, and EuS-Au composite nanocrystals were dispersed in a PMMA-containing solution. Thereafter, a thin film was formed by a casting method. The film thickness was 1 ⁇ m.
- PMMA Poly (methyl methacrylate)
- Acrylic resin (PMMA) was dissolved in chloroform, and EuS nanocrystals were dispersed in the PMMA-containing solution. Thereafter, a thin film was formed by a casting method. The film thickness was 1 ⁇ m.
- the Verde constant spectrum was measured at room temperature. The measurement results are shown in FIG.
- the horizontal axis in FIG. 20 is the wavelength, and the vertical axis is the normalized Verde constant [degOe ⁇ 1 abs ⁇ 1 ].
- the rotation angle of the polarization plane is normalized by the applied magnetic field and the absorbance.
- FIG. 20 a large change in Faraday rotation was observed in the wavelength region of the Au plasmon absorption band. That is, it was confirmed that Au plasmon affects the magneto-optical properties of EuS.
- the thin film of an Example has about twice the Faraday effect compared with the thin film of a comparative example.
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Abstract
Description
本発明の実施形態に係る複合ナノ結晶は、結晶性のEu(II)化合物ナノ粒子及び結晶性の金属ナノ粒子が複合化された複合ナノ結晶である。ここで複合ナノ結晶とは、ナノサイズの複合結晶の意味である。Eu(II)化合物ナノ粒子の大きさは、例えば平均粒径が約5nm~100nmである。Eu(II)化合物ナノ粒子の材料としては、例えば、EuO,EuS,EuSe又はEuTeのユーロピウムカルコゲナイドが用いられる。金属ナノ粒子の大きさは、例えば平均粒径が約5nm~100nmである。金属ナノ粒子の材料としては、光照射によって表面に局在電場を形成する金属材料であれば何でもよく、例えば、Ag,Au,Pt,Cu又はこれらの組み合わせが用いられる。あるいは、Ag,Au,Pt及びCuから選択される2種類以上の合金であってもよい。
実施形態に係る複合ナノ結晶の第1の製造方法について説明する。なお、以下では説明理解の容易性を考慮し、Eu(II)化合物としてEuS(硫化ユーロピウム)、金属としてAu(金)を用いた場合を説明する。
実施形態に係る複合ナノ結晶の第2の製造方法について図1~6を用いて説明する。第1の製造方法と同様に、Eu(II)化合物としてEuS、金属としてAuを用いた場合を説明する。
本発明の実施形態に係る複合薄膜は、結晶性のEu(II)化合物ナノ粒子及び結晶性の金属ナノ粒子からなる複合薄膜である。膜厚は、例えば約5nm~100μmである。Eu(II)化合物ナノ粒子の大きさは、例えば平均粒径が約5nm~100nmである。Eu(II)化合物ナノ粒子の材料としては、例えば、EuO,EuS,EuSe又はEuTeのユーロピウムカルコゲナイドが用いられる。金属ナノ粒子大きさは、例えば平均粒径が約5nm~100nmである。金属ナノ粒子の材料としては、光照射によって表面に局在電場を形成する金属であれば何でもよく、例えば、Ag,Au,Pt,Cu又はこれらの組み合わせが用いられる。あるいは、Ag,Au,Pt及びCuから選択される2種類以上の合金であってもよい。
実施形態に係る複合薄膜の製造方法について説明する。なお、以下では説明理解の容易性を考慮し、Eu(II)化合物としてEuS、金属としてAuを用いた場合を説明する。
溶媒:アセトニトリル 20ml
支持電解質:ヘキサフルオロリン酸テトラエチルアンモニウム 0.1mol/l
試料:Eu(III)ジチオカルバミド錯体 0.06mol/l
Arによる脱気:15分間
まず、上記条件で、Eu(III)からEu(II)への変化が起こるか否かを検証すべく、参照電極及び対極に印加する電圧を100mV/sで変化させ、印加電圧0~2Vの間の電流電圧特性を測定した。結果を図12に示す。図12の横軸は電圧、縦軸が電流である。図12では、溶媒に試料を入れずに測定した場合の測定結果を点線(Blank)で示しており、溶媒に試料を入れて測定した場合の測定結果を実線(Eu complex)で示している。電圧を0Vから-2.0Vに向けて変化させた場合には、下側の点線又は実線で示す結果となり、電圧を-2.0Vから0Vに向けて変化させた場合には、上側の点線又は実線で示す結果となった。このように、Eu(III)ジチオカルバミド錯体を含む溶媒に電圧を印加するほど電流が大きく流れていること、すなわちEu(III)からEu(II)へ変化していることが確認された。
上述したEu(II)化合物を含む複合ナノ結晶及び複合薄膜は、大きなファラデー効果を奏するため、光磁気材料として応用することができる。例えば、戻り光を防止するために光通信などで用いられている光アイソレータなどへの適用が考えられる。図18は、従来から用いられている光アイソレータの概略構成図である。図18に示すように、光アイソレータは、ファラデー回転子10が偏光子11と検光子12の間に置かれ、ファラデー回転子10が磁場を印加する永久磁石13に挟まれた構造となっている。光アイソレータでは、光ファイバ14aから導入された順方向の光は偏光子11により直線偏光にされた後、ファラデー回転子10により偏光面が回転した光が検光子12を通過して光ファイバ14bに導入される。一方、逆方向の光(戻り光)は検光子12により直線偏光にされ、ファラデー回転子10によりその偏光面が回転するが、回転後の光は偏光子11とは偏光面が一致しないため光は偏光子11を通過できず、戻り光がそこで遮断されるようになっている。ファラデー回転子10として、従来はガーネット結晶製のもの等を用いていた。上述したEu(II)化合物を含む複合ナノ結晶又は複合薄膜を用いてファラデー回転子10を形成した場合であっても、ガーネット結晶製のファラデー回転子10と同様の偏光面回転効果を得ることができる。このため、家庭用の短距離通信用光アイソレータを安価に作製することが可能である。
また、上述したEu(II)化合物を含む複合ナノ結晶を無機ガラス薄膜やポリマー薄膜に含有させることにより新たな特性を有する薄膜を生成することができる。例えば、上述した複合ナノ結晶を含有した溶液を、加水分解及び縮重合反応によりコロイド溶液とし、さらに反応を促進させることにより流動性を失ったゲルを形成し、このゲルを熱処理することにより、複合ナノ結晶を含有した無機ガラス薄膜を生成することができる。また、例えば、上述した複合ナノ結晶を溶解したポリマーに分散させて板等に吹き付けて乾かすことにより、複合ナノ結晶を含有したポリマー薄膜を生成することができる。
アクリル樹脂(PMMA:Poly(methyl methacrylate))をクロロホルムに溶解し、PMMA含有溶液にEuS-Au複合ナノ結晶を分散させた。その後、キャスト法にて薄膜を作成した。膜厚は、1μmであった。
アクリル樹脂(PMMA)をクロロホルムに溶解し、PMMA含有溶液にEuSナノ結晶を分散させた。その後、キャスト法にて薄膜を作成した。膜厚は、1μmであった。
実施例及び比較例について、室温においてベルデ定数スペクトルを測定した。測定結果を図20に示す。図20の横軸は波長、縦軸は規格化されたベルデ定数[degOe-1abs-1]である。ここでは、偏光面の回転角を印加磁場及び吸収度で規格化している。図20に示すように、Auプラズモン吸収バンドの波長領域においてファラデー回転の大きな変化が観測された。すなわち、AuプラズモンがEuSの光磁気特性に影響を与えることが確認された。また、実施例の薄膜は、比較例の薄膜に比べて約2倍のファラデー効果を奏することが確認された。
Claims (13)
- Eu(II)化合物ナノ粒子に金属ナノ粒子を複合化させて形成される複合ナノ結晶。
- 前記Eu(II)化合物ナノ粒子は、EuO,EuS,EuSe又はEuTeから選択される材料により形成される請求項1記載の複合ナノ結晶。
- 前記金属ナノ粒子は、Ag,Au,Pt及びCuから選択される金属材料、前記金属材料の組み合わせ、又は、Ag,Au,Pt及びCuから選択される2種類以上の合金により形成される請求項1又は2記載の複合ナノ結晶。
- 同一又は異なるチオール基、水酸基、カルボキシル基、スルホン酸基、シアノ基、アミノ基又はピリジル基を二つ以上有する化合物によって結晶性の前記Eu(II)化合物ナノ粒子と結晶性の前記金属ナノ粒子とを複合化する請求項1~3の何れか一項に記載の複合ナノ結晶。
- Eu(II)化合物ナノ粒子に金属ナノ粒子を複合化させて形成される複合薄膜。
- 請求項1~4の何れか一項に記載の複合ナノ結晶又は請求項5の記載の複合薄膜を用いて形成された光磁気材料。
- 請求項1~4の何れか一項に記載の複合ナノ結晶を含む無機ガラス薄膜。
- 請求項1~4の何れか一項に記載の複合ナノ結晶を含むポリマー薄膜。
- 請求項1~4の何れか一項に記載の複合ナノ結晶、請求項5の記載の複合薄膜、請求項6に記載の光磁気材料又は請求項7に記載の無機ガラス薄膜を用いて形成されたファラデー回転子を備える光アイソレータ。
- Eu(III)を含有する錯体を熱還元反応させることによって結晶性のEu(II)化合物ナノ粒子を合成するステップと、
金属を含有する錯体を熱還元反応させることによって結晶性の金属ナノ粒子を合成するステップと、
前記Eu(II)化合物ナノ粒子と前記金属ナノ粒子とを同一又は異なるチオール基、水酸基、カルボキシル基、スルホン酸基、シアノ基、アミノ基又はピリジル基を二つ以上有する化合物によって接合して複合ナノ結晶を合成するステップと、
を備える複合ナノ結晶の製造方法。 - Eu(III)を含有する錯体と金属を含有する錯体とを混合するステップと、
混合した錯体を熱還元反応させることによって複合ナノ結晶を合成するステップと、
を備える複合ナノ結晶の製造方法。 - 電気化学的に複合薄膜を製造する製造方法であって、
Eu(III)を含有する錯体及び金属を含有する錯体を溶媒に分散させるステップと、
透明電極を作用電極とし、前記溶媒中に前記透明電極を挿入して電圧を印加することにより前記透明電極にEu(II)化合物ナノ粒子及び金属ナノ粒子からなる複合薄膜を形成するステップと、
を備えることを特徴とする複合薄膜の製造方法。 - 電気化学的に複合薄膜を製造する製造方法であって、
Eu(III)を含有する錯体を溶媒に分散させるEu分散ステップと、
金属を含有する錯体を溶媒に分散させる金属分散ステップと、
透明電極を作用電極とし、前記溶媒中に前記透明電極を挿入して電圧を印加することによりEu(II)化合物又は金属からなる薄膜を前記透明電極に形成する薄膜形成ステップと、
を備え、
前記Eu分散ステップ、前記薄膜形成ステップ、前記金属分散ステップ及び前記薄膜形成ステップの順に実行し、又は、前記金属分散ステップ、前記薄膜形成ステップ、前記Eu分散ステップ及び前記薄膜形成ステップの順に実行すること、
を特徴とする複合薄膜の製造方法。
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DE102015008803A1 (de) | 2014-07-09 | 2016-01-14 | Electro-Motive Diesel, Inc. | Auslasssystem mit entfernt angeordneter Auslasssteuervorrichtung mit mehreren Ventilen |
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US20140055855A1 (en) | 2014-02-27 |
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JP6021113B2 (ja) | 2016-11-02 |
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