WO2015099145A1 - Luminophore et son procédé de production - Google Patents

Luminophore et son procédé de production Download PDF

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Publication number
WO2015099145A1
WO2015099145A1 PCT/JP2014/084590 JP2014084590W WO2015099145A1 WO 2015099145 A1 WO2015099145 A1 WO 2015099145A1 JP 2014084590 W JP2014084590 W JP 2014084590W WO 2015099145 A1 WO2015099145 A1 WO 2015099145A1
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phosphor
afterglow
group
element selected
composition
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PCT/JP2014/084590
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English (en)
Japanese (ja)
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純平 上田
景友 黒石
勢津久 田部
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国立大学法人京都大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials

Definitions

  • the present invention relates to a phosphor and a method for producing the phosphor.
  • Phosphorescent long afterglow phosphors temporarily trap electrons, holes, and other carriers generated by external energy (eg, ultraviolet light, purple light, etc.) into defects in the crystal, and the trapped carriers The light is gradually released by the thermal energy of the air temperature, and recombines at the emission center to show long-lasting emission.
  • This long afterglow phosphor stores sunlight energy during the day, light energy from room lighting, etc., and shines at night or after extinguishing the light, so that it can be used as a visible nocturnal paint. Therefore, the long afterglow phosphor is used for safety signs and evacuation guidance systems.
  • white LEDs Light Emitting Diodes
  • White LEDs having characteristics such as long-term stability, energy saving, and high emission quantum efficiency have been frequently used as solid-state lighting devices in place of the fluorescent lamps.
  • White LEDs that are commonly used are composed of a combination of a blue LED and a yellow phosphor, or a combination of a blue LED, a red phosphor, and a green phosphor. That is, the light from the white LED includes only blue light as light having the shortest wavelength, and does not include ultraviolet rays.
  • Ce 3+ : YAG phosphor As a phosphor that absorbs light in the blue region, a Ce 3 + -added A 3 B 2 C 3 O 12 garnet phosphor (for example, Ce 3+ : Y 3 Al 2 Al 3 O 12 , hereinafter referred to as Ce 3+ : YAG phosphor). Is known).
  • the Ce 3+ : YAG phosphor absorbs light in the blue region and exhibits yellow light emission with high quantum efficiency. Therefore, the phosphor constituting the white LED (that is, the yellow phosphor used in combination with the blue LED) ).
  • Ce 3+ : YAG does not exhibit afterglow characteristics due to blue light excitation.
  • Ce 3+ : YAGG was found to have a very low afterglow intensity (afterglow luminance) although it exhibited afterglow characteristics when the blue light was blocked after being excited with blue light.
  • an object of the present invention is to provide a phosphor excellent in long afterglow characteristics by ultraviolet excitation and excellent in long afterglow characteristics by blue light excitation, and a method for producing the same.
  • composition formula (1) A 3 B 2 C 3 O 12 (1) (Where A is (i) at least one element selected from the group consisting of Mg, Ca, Sr, La, Gd, Tb, Lu, and Y, and (ii) Ce. B is at least one element selected from the group consisting of Al, Ga, Sc, In, Mg, Lu, and Y; C is at least one element selected from the group consisting of Si, Ge, Al, and Ga).
  • At least one metal element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Hf, Si, Yb, Eu, Pr, and Tb is doped.
  • Item 3. The phosphor according to Item 1 or 2, wherein the molar ratio of the element (i) to the (ii) Ce is 0.9999: 0.0001 to 0.95: 0.05. 4).
  • the phosphor according to any one of Items 1 to 3, which is used for phosphorescent phosphors, white LEDs, phosphorescent ceramics, phosphorescent resins, phosphorescent paints, phosphorescent evacuation guidance systems, or bioimaging markers. 5.
  • Fluorescence doped with at least one metal element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Hf, Si, Yb, Eu, Pr, and Tb A method for manufacturing a body, (1) Step 1 of preparing a composition containing the element-containing compound (B), B-element-containing compound, C-element-containing compound, Ce-containing compound and the metal-element-containing compound, and (2) 1200 of the composition. Heating process at ⁇ 1800 °C 2 In order.
  • long afterglow refers to a long period of time (eg, several) even if the excitation light (eg, ultraviolet light, violet light, blue light, etc.) is irradiated and then the excitation light is cut off (stopped).
  • the excitation light eg, ultraviolet light, violet light, blue light, etc.
  • Min. To several tens of hours or more refers to continuous light emission, and can be clearly distinguished from the time scale of light emission (ns to ms) indicated by the electronic transition of atoms.
  • the phosphor having the long afterglow function is also referred to as “long afterglow phosphor”, and the phosphor of the present invention is a long afterglow phosphor.
  • the center wavelength (emission peak) of afterglow is about 480 to 700 nm (green to red).
  • phosphorescence means storing (collecting or trapping) carriers such as electrons and holes so as to accumulate (accumulate) light.
  • the carrier is generated by external energy such as ultraviolet light, purple light, and blue light, is captured by the trap, and emits light by being released by the thermal energy of the outside air.
  • blue light refers to visible light having a wavelength of 400 to 460 nm unless otherwise specified.
  • ultraviolet light means ultraviolet light having a wavelength of 200 to 380 nm unless otherwise specified.
  • room temperature means that the air temperature is 10 to 30 ° C. unless otherwise specified.
  • the phosphor of the present invention has the following composition formula (1): A 3 B 2 C 3 O 12 (1) (Where A is (i) at least one element selected from the group consisting of Mg, Ca, Sr, La, Gd, Tb, Lu, and Y, and (ii) Ce. B is at least one element selected from the group consisting of Al, Ga, Sc, In, Mg, Lu, and Y; C is at least one element selected from the group consisting of Si, Ge, Al, and Ga). At least one metal element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Hf, Si, Yb, Eu, Pr, and Tb is doped. It is characterized by.
  • the phosphor of the present invention having the above-described characteristics can be obtained by, in particular, ultraviolet excitation by doping a specific garnet crystal phosphor containing a Ce element with a specific metal element (the specific metal element is also referred to as an M element). Excellent long afterglow characteristics and excellent long afterglow characteristics by blue light excitation.
  • the phosphor of the present invention is also excellent in water resistance.
  • the phosphor of the present invention is also referred to as Ce and a specific metal element co-added garnet crystal phosphor.
  • a schematic diagram of the garnet crystal structure and occupied cations is shown in FIG.
  • a composition of a general garnet crystal structure (garnet structure) is represented by the composition formula (1): A 3 B 2 C 3 O 12 .
  • the cation of the element (A element) represented by A in the above formula (1) occupies a dodecahedron site, and the cation of the element (B element) represented by B in the above formula (1) occupies an octahedral site.
  • the cation of the element (C element) represented by C in the above formula (1) occupies a tetrahedral site.
  • the phosphor of the present invention is a phosphor obtained by co-adding Ce and M elements in the garnet crystal as a base crystal.
  • Ce of A in the above formula (1) means that it contains Ce 3+ as the emission center, and this Ce 3+ occupies a dodecahedron site.
  • the cations of the M element mainly occupy octahedral sites in many cases.
  • the garnet structure in the phosphor of the present invention may have a solid solution region.
  • lattice defects and antisite defects occur in the crystal, and a slight composition ratio deviation may occur with respect to the above formula (1) (that is, the phosphor of the present invention has the above formula (1)).
  • the present invention may have a non-stoichiometric composition (which may have a non-stoichiometric (non-chemical) stoichiometric composition).
  • the crystal structure of the phosphor of the present invention can be confirmed by an X-ray diffraction method or the like.
  • the element A is (i) at least one element selected from the group consisting of Mg, Ca, Sr, La, Gd, Tb, Lu, and Y, and (ii) Ce.
  • the cation of A (the cation of the element (i) and the cation of (ii) Ce) is in the 8-coordinate position and occupies a dodecahedron site (the site is also referred to as A site).
  • At least one element selected from the group consisting of Lu, Gd and Y is preferable, and Y is more preferable.
  • Ce 3+ has strong broad absorption due to 4f-5d permissible transition and high luminous efficiency. Further, the Ce 3+ 5d level is reduced in energy by a centroid shift due to the electron cloud expansion effect, and is split into a plurality of levels in the host structure due to the influence of the crystal field.
  • FIG. 2 shows changes in the band structure depending on the composition of the garnet crystal structure. Since the phosphor of the present invention uses a garnet crystal structure as a host, the 5d orbit of Ce 3+ is split into five, and the split width depends on the garnet crystal composition. Therefore, as described above, it is possible to change the optical characteristics (light emission color) of Ce 3+ by changing the garnet crystal composition.
  • the center wavelength of afterglow originating from Ce 3+ varies depending on the garnet crystal composition and is mainly in the range of 500 nm to 550 nm.
  • the B element B is at least one element selected from the group consisting of Al, Ga, Sc, In, Mg, Lu, and Y.
  • the cation of B occupies a hexacoordinate octahedral site (the site is also referred to as B site).
  • B can use 1 type, or 2 or more types of elements.
  • At least one element selected from the group consisting of Al and Ga is preferable.
  • the C element C is at least one element selected from the group consisting of Si, Ge, Al, and Ga.
  • the C cation is in a tetracoordinate position and occupies a tetrahedral site (the site is also referred to as a C site).
  • C can use 1 type, or 2 or more types of elements.
  • the cation of the element is a tetravalent cation
  • From the viewpoint of electrical neutrality it is necessary to use an element that becomes a divalent cation as the element to be represented.
  • At least one element selected from the group consisting of Al and Ga is preferable, and Ga is more preferable.
  • both B and C are at least one element selected from the group consisting of Al and Ga (that is, the phosphor of the present invention has the following composition formula (2): A 3 (Al, Ga) 2 (Al, Ga) 3 O 12 (2) [A is the same as above. ]
  • the relationship between the number of moles of Ga / (total number of moles of B and C) and the afterglow characteristics due to blue light excitation in the case where the compound represented by the above formula is a phosphor in which the M element is doped) will be described. .
  • the phosphor of the present invention is irradiated with excitation light, Ce 3+ as an emission center is excited to an excitation level, and the excited electron returns to a level lower than the excitation level.
  • a phenomenon in which energy is emitted as light when the excited electrons return to the level is light emission.
  • the electrons of Ce 3+ are trapped in an electron trap (where electrons can be temporarily stored), the electrons receive thermal energy of the temperature, and then jump out of the electron trap to return to the original Ce.
  • the phenomenon of light emission when returning to 3+ is afterglow. Therefore, efficiently transporting the electrons of Ce 3+ to the electron trap leads to long-time persistence characteristics.
  • the Ga composition ratio in the phosphor of the present invention is set so that the number of moles of Ga / (total number of moles of B and C) is 0.5 to 0.8. It is preferable.
  • the phosphor of the present invention is at least one metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Hf, Si, Yb, Eu, Pr and Tb.
  • the element is doped.
  • the metal element M newly forms the above-described electron trap as a co-doped ion.
  • the said M element can use 1 type, or 2 or more types of the said metal element.
  • At least one selected from the group consisting of Cr, Ni, Fe, V, Yb and Si is preferable, and at least one selected from the group consisting of Cr, Ni, Yb and Si is more preferable, At least one selected from the group consisting of Cr and Yb is more preferable, and Cr is particularly preferable.
  • the doping amount of the M element is preferably 0.001 to 5 mol%, more preferably 0.01 to 1 mol%, still more preferably 0.05 to 0.5 mol% with respect to the compound represented by the above formula (1).
  • the doping amount of the M element is within the above range, the afterglow intensity does not decrease, and the long afterglow characteristics due to ultraviolet excitation and blue light excitation are further improved.
  • a phosphor in which 0.001 to 5 mol% of Cr is doped with respect to the compound (also referred to as a Cr co-doped phosphor) is preferable.
  • the center wavelength of afterglow in this Cr co-doped phosphor is 510 nm corresponding to the center wavelength of afterglow originating from Ce 3+ from the garnet crystal composition of the phosphor and is easily visible to the human eye. Further, since Cr 3+ persists even in the vicinity of 700 nm, it is also useful as an afterglow phosphor for bioimaging.
  • a phosphor in which 0.001 to 5 mol% of Ni is doped with respect to the compound (also referred to as Ni co-doped phosphor) is preferable.
  • the center wavelength of afterglow in this Ni co-doped phosphor is 510 nm corresponding to the center wavelength of afterglow originating from Ce 3+ from the garnet crystal composition of the phosphor and is easily visible to the human eye.
  • a phosphor in which 0.001 to 5 mol% Fe is doped with respect to the compound also referred to as Fe co-doped phosphor
  • the center wavelength of afterglow in this Fe co-doped phosphor is 510 nm corresponding to the center wavelength of afterglow originating from Ce 3+ from the garnet crystal composition of the phosphor, and is easily visible to the human eye.
  • a phosphor in which 0.001 to 5 mol% of Mn is doped with respect to the compound also referred to as a Mn co-doped phosphor
  • this Mn co-doped phosphor has an afterglow center wavelength originating from Mn ions at 700 nm, it is effective for application to bioimaging described later.
  • the state, shape, size and the like of the phosphor of the present invention are not particularly limited, and may be set as appropriate according to the purpose of use.
  • the state includes single crystal, polycrystal (translucent ceramic), and the shape includes powder, pellets, and the like.
  • the average particle size of the powder is preferably about 0.5 to 50 ⁇ m.
  • a known method may be adopted, and for example, a measuring method using an apparatus using a light scattering method may be mentioned.
  • the crystal structure of the phosphor of the present invention may be single crystal or polycrystal as described above.
  • composition formula (1) A 3 B 2 C 3 O 12 (1) (Where A is (i) at least one element selected from the group consisting of Mg, Ca, Sr, La, Gd, Tb, Lu, and Y, and (ii) Ce. B is at least one element selected from the group consisting of Al, Ga, Sc, In, Mg, Lu, and Y; C is at least one element selected from the group consisting of Si, Ge, Al, and Ga).
  • Fluorescence doped with at least one metal element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Hf, Si, Yb, Eu, Pr, and Tb A method for manufacturing a body, (1) Step 1 of preparing a composition containing the element-containing compound (B), B-element-containing compound, C-element-containing compound, Ce-containing compound and the metal-element-containing compound, and (2) 1200 of the composition. Heating process at ⁇ 1800 °C 2 Manufacturing method including, in order, Is mentioned.
  • a composition comprising the element-containing compound (i), a B element-containing compound, a C element-containing compound, a Ce-containing compound and the metal element (M element) -containing compound ( Compound-containing composition) is prepared.
  • the compound include oxides, hydroxides, halides (chlorides, fluorides, etc.), nitrates, oxalates, carbonates, sulfates, and the like. What is necessary is just to determine suitably the usage-amount of each compound other than the M element containing compound in the said composition so that the composition of the fluorescent substance finally obtained may satisfy the said composition formula (1).
  • the amount of the M element-containing compound used may be appropriately determined according to the intended use or the like (Note that the amount of the M element-containing compound used is a compound in which the doping amount of the M element is represented by the above formula (1)). It is preferably used in an amount of 0.001 to 5 mol%, more preferably 0.01 to 1 mol%, still more preferably 0.05 to 0.5 mol%).
  • the compound represented by the above formula (1) is used. Determine the amount of the element-containing compound, B element-containing compound, C element-containing compound and Ce-containing compound of (i) so as to have a stoichiometric composition (according to the stoichiometric composition represented by the above formula (1)). Furthermore, the usage amount of the M element-containing compound is determined. After preparing the composition containing the said each compound, the fluorescent substance of this invention is obtained by heating (baking) the said composition at the following process 2. FIG. The obtained garnet structure in the phosphor of the present invention may have a solid solution region.
  • Examples of the element-containing compound (i) include oxides, hydroxides, halides, nitrates, oxalates, carbonates and sulfates containing the element (i).
  • the element-containing compound (i) can be used alone or in combination of two or more.
  • oxide containing the element (i) examples include MgO, CaO, SrO, La 2 O 3 , Gd 2 O 3 , Tb 4 O 7 , Lu 2 O 3 , Y 2 O 3, etc.
  • the hydrate can also be used.
  • hydroxide containing the element (i) examples include Mg (OH) 2 , Ca (OH) 2 , Sr (OH) 2 , La (OH) 3 , Gd (OH) 3 , and Tb (OH) 3. , Lu (OH) 3 , Y (OH) 3 and the like, and hydrates thereof can also be used.
  • examples of the chloride include MgCl 2 , CaCl 2 , SrCl 2 , LaCl 3 , GdCl 3 , TbCl 3 , LuCl 3 , YCl 3 and the like. Japanese products can also be used.
  • nitrate containing the element (i) examples include Mg (NO 3 ) 2 , Ca (NO 3 ) 2 , Sr (NO 3 ) 2 , La (NO 3 ) 3 , Gd (NO 3 ) 3 , Tb ( NO 3 ) 3 , Lu (NO 3 ) 3 , Y (NO 3 ) 3 and the like, and hydrates thereof can also be used.
  • oxalate containing an element of (i), MgC 2 O 4 , CaC 2 O 4, SrC 2 O 4, La 2 (C 2 O 4) 3, Gd 2 (C 2 O 4) 3, Tb 2 (C 2 O 4) 3, Lu 2 (C 2 O 4) 3, Y 2 (C 2 O 4) 3 and the like it can also be used these hydrates.
  • Examples of the carbonate containing the element (i) include MgCO 3 , CaCO 3 , SrCO 3 , La 2 (CO 3 ) 3 , Gd 2 (CO 3 ) 3 , Tb 2 (CO 3 ) 3 , Lu 2 ( CO 3) 3, Y 2 ( CO 3) 3 and the like, can also be used these hydrates.
  • the carbonate includes a bicarbonate such as Ca (HCO 3 ) 2 .
  • Examples of the sulfate containing the element (i) include MgSO 4 , CaSO 4 , SrSO 4 , La 2 (SO 4 ) 3 , Gd 2 (SO 4 ) 3 , Tb 2 (SO 4 ) 3 , Lu 2 ( SO 4) 3, Y 2 ( SO 4) 3 and the like, it can also be used these hydrates.
  • B element-containing compound examples include B element-containing oxides, hydroxides, halides, nitrates, oxalates, carbonates, sulfates, and the like.
  • the B element-containing compound can be used alone or in combination of two or more.
  • oxide containing B element examples include Al 2 O 3 , Ga 2 O 3 , Sc 2 O 3 , In 2 O 3 , MgO, Lu 2 O 3 , Y 2 O 3, and the like. Things can also be used.
  • hydroxide containing B element Al (OH) 3 , Ga (OH) 3 , Sc (OH) 3 , In (OH) 3 , Mg (OH) 2 , Lu (OH) 3 , Y (OH) 3 ), etc., and these hydrates can also be used.
  • examples of the chloride include AlCl 3 , GaCl 3 , ScCl 3 , InCl 3 , MgCl 2 , LuCl 3 , YCl 3, etc., and these hydrates may also be used. it can.
  • the nitrate containing B element includes Al (NO 3 ) 3 , Ga (NO 3 ) 3 , Sc (NO 3 ) 3 , In (NO 3 ) 3 , Mg (NO 3 ) 2 , and Lu (NO 3 ) 3. , Y (NO 3 ) 3 and the like, and these hydrates can also be used.
  • Al 2 (C 2 O 4 ) 3 , Ga 2 (C 2 O 4 ) 3 , Sc 2 (C 2 O 4 ) 3 , In 2 (C 2 O 4 ) 3 MgC 2 O 4 , Lu 2 (C 2 O 4 ) 3 , Y 2 (C 2 O 4 ) 3 and the like, and hydrates thereof can also be used.
  • Examples of the carbonate containing B element include Al 2 (CO 3 ) 3 , Ga 2 (CO 3 ) 3 , Sc 2 (CO 3 ) 3 , In 2 (CO 3 ) 3 , MgCO 3 , Lu 2 (CO 3 ) 3 , Y 2 (CO 3 ) 3 and the like, and hydrates thereof can also be used.
  • the sulfate containing B element includes Al 2 (SO 4 ) 3 , Ga 2 (SO 4 ) 3 , Sc 2 (SO 4 ) 3 , In 2 (SO 4 ) 3 , MgSO 4 , Lu 2 (SO 4 ) 3 , Y 2 (SO 4 ) 3 and the like, and these hydrates can also be used.
  • C element-containing compounds include oxides, hydroxides, halides (chlorides, fluorides, etc.), nitrates, oxalates, carbonates, sulfates and the like containing C elements.
  • the C element-containing compound can be used alone or in combination of two or more.
  • oxide containing C element examples include SiO 2 , GeO 2 , Al 2 O 3 , and Ga 2 O 3 , and these hydrates can also be used.
  • hydroxide containing C element examples include Si (OH) 4 , Ge (OH) 4 , Al (OH) 3 , Ga (OH) 3, and the like, and these hydrates can also be used. .
  • examples of the chloride include SiCl 4 , GeCl 4 , AlCl 3 , GaCl 3, etc., and hydrates thereof can also be used.
  • nitrates containing C element examples include Si (NO 3 ) 4 , Ge (NO 3 ) 4 , Al (NO 3 ) 3 , Ga (NO 3 ) 3 , and the use of these hydrates. Can do.
  • Examples of the oxalate containing the C element include Si (C 2 O 4 ) 2 , Ge (C 2 O 4 ) 2 , Al 2 (C 2 O 4 ) 3 , Ga 2 (C 2 O 4 ) 3 and the like. These hydrates can also be used.
  • Ce-containing compound examples include Ce-containing oxides, hydroxides, halides (chlorides, fluorides, etc.), nitrates, oxalates, carbonates, sulfates, and the like. Specifically, CeO 2 , Ce 2 O 3 , Ce (OH) 3 , CeCl 3 , Ce (NO 3 ) 3 , Ce 2 (C 2 O 4 ) 3 , Ce 2 (CO 3 ) 3 , Ce 2 ( SO 4 ) 3 , Ce (SO 4 ) 2 and the like, and hydrates of these can also be used.
  • the Ce-containing compound can be used alone or in combination of two or more.
  • Examples of the metal element (M element) -containing compound include M as a metal component, such as a metal oxide, a metal hydroxide, a metal halide, a metal nitrate, a metal oxalate, a metal carbonate, and a metal sulfate.
  • M a metal component
  • a metal element containing compound (M element containing compound) can be used by 1 type or in combination of 2 or more types.
  • metal halides include TiCl 3 , TiCl 4 , VCl 2 , VCl 3 , VCl 4 , VCl 5 , CrCl 2 , CrCl 3 , MnCl 2 , FeCl 2 , FeCl 3 , CoCl 2 , NiCl 2 , CuCl, CuCl 2 , ZnCl 2, ZrCl 2, ZrCl 4 , HfCl 4, SiCl 3, Si 3 Cl 8, Si 4 Cl 10, Si 5 Cl 12, Si 6 Cl 12, YbCl 3, EuCl 3, PrCl 3, TbCl 3 , etc.
  • Metal nitrates include Ti (NO 3 ) 4 , V (NO 3 ) 5 , Cr (NO 3 ) 3 , Mn (NO 3 ) 2 , Fe (NO 3 ) 2 , Fe (NO 3 ) 3 , Co (NO 3 ) 2 , Ni (NO 3 ) 2 , Cu (NO 3 ) 2 , Zn (NO 3 ) 2 , Zr (NO 3 ) 2 , Zr (NO 3 ) 4 , Hf (NO 3 ) 4 , Yb (NO 3) ) 3 , Eu (NO 3 ) 3 , Pr (NO 3 ) 3 , Tb (NO 3 ) 3 and the like, and these hydrates can also be used.
  • metal carbonate examples include CrCO 3 , MnCO 3 , FeCO 3 , CoCO 3 , NiCO 3 , Cu 2 CO 3 , ZnCO 3 , ZrCO 3 , Yb 2 (CO 3 ) 3 , Eu 2 (CO 3 ) 3 , Pr 2. (CO 3) 3, Tb 2 (CO 3) 3 and the like, it can also be used these hydrates.
  • Metal sulfates Ti (SO 4) 2, V 2 (SO 4) 5, CrSO 4, MnSO 4, FeSO 4, CoSO 4, NiSO 4, CuSO 4, ZnSO 4, ZrSO 4, Zr (SO 4) 2 , Yb 2 (SO 4 ) 3 , Eu 2 (SO 4 ) 3 , Pr 2 (SO 4 ) 3 , Tb 2 (SO 4 ) 3 and the like, and these hydrates can also be used.
  • the compound-containing composition may be pulverized as necessary.
  • the pulverization method include wet pulverization methods such as a medium stirring mill, colloid mill, and wet ball mill; dry pulverization methods such as a jet mill, a dry ball mill, and a roll crusher.
  • wet pulverization method water, an organic solvent (for example, methanol, ethanol, etc.) and the like are mixed with the compound-containing composition, and then each compound in the compound-containing composition can be pulverized.
  • a plurality of pulverization methods may be used in combination.
  • the compound-containing composition may be subjected to classification, chemical treatment, drying or the like, if necessary.
  • the compound-containing composition may contain a sintering aid.
  • a sintering aid examples include boric acid, boron oxide, colloidal silica, and TEOS (tetraethyl orthosilicate).
  • step 2 the compound-containing composition prepared in step 1 is heated (baked) at 1200 to 1800 ° C.
  • the compound-containing composition is put into a crucible such as aluminum oxide or magnesium oxide and heated.
  • the heating temperature is preferably 1500 to 1600 ° C.
  • the heating time is preferably 3 to 24 hours.
  • the atmosphere for heating may be any of an air atmosphere, a reducing atmosphere, and a vacuum atmosphere, but heating is preferably performed in a vacuum atmosphere.
  • step 2 Before performing the heating in step 2, if necessary, temporary baking may be performed. By performing the preliminary firing, evaporation of Ga can be prevented.
  • the temperature at the time of pre-baking is preferably 1000 to 1400 ° C.
  • step 2 single crystallization, pulverization, water resistance treatment, etc. may be performed by the floating zone method.
  • a polycrystalline sample rod is used as a raw material.
  • a part of the sample rod is heated to create a melted portion between the lower single crystal that becomes the seed crystal and the sample rod, and the melt portion (in the melted portion) is subjected to surface tension.
  • This is a method of cooling the melt part by moving the whole downward while supporting the melt.
  • the heating method is not particularly limited, and examples include heating with a halogen lamp.
  • the same method as the pulverization method in the above step 1 may be mentioned.
  • Water resistance treatment includes a method of surface coating with an organic material or an inorganic material.
  • the phosphor of the present invention can be applied to phosphorescent phosphors, white LEDs, phosphorescent ceramics, phosphorescent resins, phosphorescent paints, phosphorescent evacuation guidance systems, bioimaging and the like.
  • a phosphorescent phosphor As an application to a phosphorescent phosphor, it can be used as a green afterglow phosphor, a yellow afterglow phosphor, etc. under white LED illumination. Specifically, there are warning lights; clock dials; lighting for evacuation guidance when facilities lighting, guide lights, etc. cannot be used due to a power failure or the like.
  • white LEDs includes mounting the phosphor of the present invention on a white LED device to obtain a lighting device that shines faintly even after it is turned off.
  • phosphorescent paint As an application to phosphorescent paint, it can be used as a visible luminous paint for dials and evacuation signs.
  • the metal M ion (Cr 3+ , Mn 2+ , Mn 4+, etc.) in the phosphor of the present invention is appropriately selected to show afterglow in the near infrared, and as a fluorescent marker A near infrared long afterglow phosphor is obtained.
  • the near-infrared long afterglow phosphor has a wavelength that is well transmitted by cells of the human body, and furthermore, the excitation light for the image can be irradiated before the human body injection, thus preventing autofluorescence and scattering of the excitation light, As a result, an imaging image with less noise can be obtained.
  • the phosphor of the present invention is excellent in long afterglow characteristics by ultraviolet excitation and long afterglow characteristics by blue light excitation because a specific metal element is doped in a specific garnet crystal phosphor containing Ce element. Excellent.
  • the phosphor of the present invention emits green to red (center wavelength is about 480 to 700 nm) upon excitation by irradiation with excitation light such as ultraviolet light and blue light, and particularly green to yellow (center wavelength is 480). (Approx. 560nm) is remarkable, so it is easy for human eyes to see. Therefore, the phosphor of the present invention can be applied to various uses (phosphorescent phosphor, white LED, phosphorescent ceramics, phosphorescent resin, phosphorescent paint, phosphorescent evacuation guidance system, bioimaging, etc.).
  • 2 shows X-ray diffraction patterns (using CuK ⁇ rays) in the phosphors of Examples 2 and 3.
  • FIG. Further, an X-ray diffraction pattern (using CuK ⁇ rays) of (Y 0.995 Ce 0.005 ) 3 Al 2 Ga 3 O 12 of Comparative Example 1 is shown.
  • ⁇ is literature data of Y 3 Al 2 Ga 3 O 12 .
  • 2 shows a fluorescence excitation spectrum in Example 1.
  • the excitation spectrum was measured using a fluorescence spectrophotometer (RF5300) manufactured by Shimadzu Corporation.
  • the upper spectrum is an excitation spectrum obtained by monitoring Ce 3+ emission at 520 nm
  • the lower spectrum is an excitation spectrum obtained by monitoring emission of Cr 3+ at 690 nm. It can be seen that both Ce 3+ emission and Cr 3+ emission can be efficiently excited by ultraviolet and blue light.
  • the fluorescence spectrum and afterglow spectrum (after 5 minutes) in Example 1 are shown.
  • This spectrum was measured by using a luminance measurement system manufactured by Konica Minolta Co., Ltd., using 460 nm obtained by spectrally separating a xenon lamp light source (MAX302) manufactured by Asahi Spectroscopy Co., Ltd. with a bandpass filter. Strong emission of Ce 3+ (520 nm) and Cr 3+ (700 nm) was observed in both emission and afterglow spectra.
  • FIG. 10 shows an afterglow spectrum by ultraviolet storage in Example 17. FIG. Almost no afterglow of Ce 3+ was observed, and only 700m strong afterglow of Mn ions was observed.
  • ⁇ em 505 nm
  • ⁇ ex 350 nm
  • Comparative Example 1 only emission from 500 nm Ce 3+ was observed.
  • the results of thermoluminescence measurements on the phosphors of Examples 1, 4, and 5 and Comparative Example 1 are shown.
  • the thermoluminescence measurement result in the fluorescent substance of Example 1 and 3 is shown.
  • the phosphors of Examples 6 to 16 were (a) under white LED illumination, (b) afterglow characteristics immediately after the UV lamp was shut off (room temperature), (c) afterglow characteristics immediately after the white LED illumination was shut off (room temperature), and ( d) A photograph showing the afterglow characteristics immediately after shutting off the white LED lighting (150 ° C). All the phosphors of Examples 6 to 16 exhibit afterglow after ultraviolet excitation and after blue light excitation by LED illumination. The thermoluminescence measurement result in the fluorescent substance of Example 18 is shown.
  • Example 1 The following raw material powders and 30 ml of ethanol were mixed using a ball mill (product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.) to obtain a mixture. Next, the mixture was calcined at 1200 ° C. for 6 hours using an electric furnace (product name KBF314N1, manufactured by Koyo Thermo System Co., Ltd.), and then further using an electric furnace (product name KBF314N1, manufactured by Koyo Thermo System Co., Ltd.). The main calcination was performed at 1600 ° C. for 24 hours. In addition, this baking was performed in the atmospheric condition.
  • a ball mill product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.
  • the excitation spectrum of the phosphor of Example 1 was measured using a fluorescence spectrophotometer (RF5300) manufactured by Shimadzu Corporation.
  • FIG. 4 shows the fluorescence excitation spectrum in Example 1.
  • FIG. 4 shows that both Ce 3+ emission and Cr 3+ emission can be efficiently excited by ultraviolet and blue light.
  • the fluorescence spectrum and afterglow spectrum of the phosphor of Example 1 were measured. 460 nm obtained by spectrally separating a xenon lamp light source (MAX302) manufactured by Asahi Spectroscopic Co., Ltd. with a bandpass filter was used as an excitation light source, and emission and afterglow spectra were measured using a luminance measurement system manufactured by Konica Minolta.
  • FIG. 5 shows the fluorescence spectrum and afterglow spectrum (after 5 minutes) in Example 1. Strong emission of Ce 3+ (520 nm) and Cr 3+ (700 nm) was observed in both emission and afterglow spectra.
  • FIG. 3 shows an X-ray diffraction pattern (using CuK ⁇ rays) in the phosphor of Example 2.
  • Example 3 The following raw material powders and 30 ml of ethanol were mixed using a ball mill (product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.) to obtain a mixture. Next, the mixture was calcined at 1200 ° C. for 6 hours using an electric furnace (product name KBF314N1, manufactured by Koyo Thermo Systems Co., Ltd.), and then a vacuum tubular electric furnace (product name VF-1800, manufactured by Crystal Systems Co., Ltd.). ) And then calcined at 1600 ° C. for 24 hours. The main firing was performed in a vacuum atmosphere.
  • a ball mill product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.
  • the phosphor of Example 5 was obtained by doping Fe into a compound having a total number of moles of C and Ga (Ga) of 0.6]. The amount of Fe doped was 0.3 mol% with respect to the compound.
  • each metal element M in Examples 6 to 16 was 0.1 mol% with respect to the compound.
  • V 2 O 5 manufactured by Aldrich
  • Example 17 The following raw material powders and 30 ml of ethanol were mixed using a ball mill (product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.) to obtain a mixture. The mixture was then fired for 24 hours in a tubular electric furnace (product name VF-1800, manufactured by Crystal Systems Co., Ltd.) in an N2-H2 (5%) atmosphere.
  • a ball mill product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.
  • FIG. 6 shows an afterglow spectrum by ultraviolet storage in Example 17. Almost no afterglow of Ce 3+ was observed, and only 700m strong afterglow of Mn ions was observed.
  • Example 18 The following raw material powders and 30 ml of ethanol were mixed using a ball mill (product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.) to obtain a mixture. Subsequently, the mixture was fired at 1600 ° C. for 12 hours using an electric furnace (product name KBF314N1, manufactured by Koyo Thermo System Co., Ltd.). The firing was performed in a vacuum atmosphere.
  • a ball mill product name premium line P-7, manufactured by Fritsch, manufactured by Fritsch Japan Ltd.
  • the phosphor has a composition of (Y 0.995 Ce 0.005 ) 3 Al 1.5 Ga 3.5 O 12 [Number of moles of Ga / (total number of moles of B (Al and Ga) and C (Ga)) is 0.7] It can also be said that the compound represented by the formula is a phosphor in which 0.15 mol% of Yb is doped.
  • FIG. 3 shows an X-ray diffraction pattern (using CuK ⁇ rays) in the phosphor of Comparative Example 1.
  • Reference example 1 A phosphor of SrAl 2 O 4 : Eu 2+ -Dy 3+ (GLL-300FFS, manufactured by Nemoto Special Chemical Co., Ltd.) was prepared.
  • Test example 1 Thermoluminescence measurement
  • the phosphors obtained in Examples 1, 3 to 5 and 18 and Comparative Example 1 were formed into pellets. Specifically, the above phosphors were compression molded at 50 MPa using a pellet molding machine (product name NT-50H, manufactured by Sansho Industry Co., Ltd.) to form pellets having a diameter of 10 mm and a thickness of 2 mm. .
  • a pellet molding machine product name NT-50H, manufactured by Sansho Industry Co., Ltd.
  • thermoluminescence measurement was performed on each phosphor. Specifically, each sample was irradiated with excitation light (ultraviolet light of 250 nm to 400 nm), and after the irradiation was cut off, the emission luminance was measured while raising the temperature of each sample from 100K. This measurement makes it possible to observe at which temperature each sample has the best afterglow characteristics.
  • excitation light ultraviolet light of 250 nm to 400 nm
  • the phosphor of Example 1 (doped M element: Cr, B in the above formula (1) is Al, C in the above formula (1) is Ga, and the moles of Ga. Number / (total number of moles of B and C) is 0.6), whereas a large peak was observed around 300K, whereas the phosphor of Example 3 (doped M element: Cr, the above formula (1)) A large peak was observed in the vicinity of 330K, with B in Al and C in the above formula (1) being Al and Ga, the number of moles of Ga / (total number of moles of B and C) being 0.5).
  • the glow peak can be shifted to the high temperature side. It was revealed that the initial intensity and afterglow duration at room temperature can be set as appropriate. 9, the electron trap depth of the phosphor of Example 1 was estimated to be 0.59 eV, and the electron trap depth of the phosphor of Example 3 was estimated to be 0.65 eV.
  • Test example 2 Measurement of afterglow luminance after ultraviolet light irradiation
  • the phosphors obtained in Examples 1 to 3, Comparative Example 1 and Reference Example 1 were formed into pellets having a diameter of 10 mm and a thickness of 2 mm by the same method as in Test Example 1.
  • excitation light (ultraviolet light 360 nm) was irradiated to each of the above-mentioned pellet-shaped phosphors, and afterglow luminance was measured 5 minutes, 20 minutes, and 1 hour after the irradiation was cut off.
  • a shutter was placed in front of the detector for baseline measurement, and the shutter was closed after 120 minutes.
  • Test example 3 Measurement of afterglow luminance after blue light irradiation Except for irradiating blue light (460 nm) instead of ultraviolet light (360 nm) as excitation light, the afterglow luminance of each of the above-mentioned pellet-shaped phosphors (blocking blue light irradiation was interrupted) in the same manner as in Test Example 2. The afterglow brightness after 5 minutes, 20 minutes and 1 hour was measured.
  • the phosphors of Examples 1 to 3 are excellent in long afterglow characteristics due to ultraviolet light excitation and also excellent in long afterglow characteristics due to blue light excitation.
  • the phosphors of Examples 1 to 3 have an extremely high afterglow luminance after one hour after blocking the excitation by blue light as compared with Reference Example 1. This is due to the generation of electron traps by co-doped ions (M) and the translucency of the sample.
  • Blue light (460 nm) is an emission wavelength of a general-purpose InGaN blue LED, and is generally used for a white LED realized by a blue LED + yellow phosphor, and is therefore optimal as an excitation wavelength of blue light.
  • Test Example 4 (Afterglow decay curve evaluation after blue light irradiation) The phosphors obtained in Examples 1 to 3 were pelletized by the same method as in Test Example 1. Next, each pellet-like phosphor was irradiated with excitation light (blue light 460 nm), and afterglow decay curves of each pellet-like phosphor after the irradiation was cut off were measured. From the afterglow decay curve, a time (afterglow time) when the afterglow luminance was less than 2 mcd / m 2 was obtained. ⁇ Each condition of Test Example 4> Excitation light source: Product name MAX302 Asahi Spectral Co., Ltd.
  • Afterglow luminance measurement device Product name Luminance measurement system, manufactured by Konica Minolta Co., Ltd. ⁇ Excitation light irradiation time: 5 minutes ⁇ Baseline measurement: 120 minutes Rear, temperature: 25 °C As a result, the afterglow time in Example 1 was 265 minutes, the afterglow time in Example 2 was 485 minutes, and the afterglow time in Example 3 was 792 minutes, both of which have excellent long afterglow characteristics due to blue light excitation. It was shown that
  • Test Example 5 Afterglow characteristics evaluation after ultraviolet light irradiation
  • the phosphors obtained in Examples 6 to 16 and Comparative Example 1 were formed into pellets having a diameter of 10 mm and a thickness of 2 mm by the same method as in Test Example 1.
  • excitation light (ultraviolet light 360 nm) was irradiated to each of the above-mentioned pellet-shaped phosphors, and afterglow characteristics (light storage characteristics) of each phosphor immediately after the irradiation was cut off were visually evaluated.
  • the evaluation criteria are as follows. The afterglow characteristics due to ultraviolet excitation of the phosphors obtained in Examples 6 to 16 are shown in FIG. 10 below.
  • Test Example 6 Evaluation of afterglow characteristics after blue light irradiation
  • the afterglow characteristics (phosphorescence characteristics) of each of the above-mentioned pellet-shaped phosphors are the same as in Test Example 5, except that a white LED containing blue light (460 nm) is used instead of ultraviolet light (360 nm) as excitation light. Was visually evaluated.
  • the evaluation criteria are the same as in Test Example 5.
  • Test Examples 5 and 6 are shown in Table 2 below. ⁇ Each condition of Test Example 6> ⁇ Excitation light irradiation time: 5 minutes ⁇ Air temperature: Room temperature (25 °C) and 150 °C
  • the phosphors of Examples 6 to 16 are excellent in long afterglow characteristics due to ultraviolet light excitation and also excellent in long afterglow characteristics due to blue light excitation.

Abstract

La présente invention a pour objet : un luminophore ayant excellentes propriétés de longue persistance lors de l'excitation par un rayon ultraviolet et ayant également d'excellentes propriétés de longue persistance lors de l'excitation par de lumière bleue; et un procédé pour la production du luminophore. Le luminophore selon la présente invention est caractérisé en ce qu'il est produit par dopage d'un composé représenté par la formule de composition (1) : A3B2C3O12 (dans laquelle A représente (i) au moins un élément choisi dans le groupe constitué par Mg, Ca, Sr, La, Gd, Tb, Lu et Y et (ii) Ce; B représente au moins un élément choisi dans le groupe constitué par Al, Ga, Sc, In, Mg, Lu et Y; et C représente au moins un élément choisi dans le groupe constitué par Si, Ge, Al et Ga) avec au moins un élément métallique choisi dans le groupe constitué par Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Hf, Si, Yb, Eu, Pr et Tb.
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