WO2012020704A1 - Matériau fluorescent d'oxyde inorganique et film fin de matériau à fluorescence blanche - Google Patents

Matériau fluorescent d'oxyde inorganique et film fin de matériau à fluorescence blanche Download PDF

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WO2012020704A1
WO2012020704A1 PCT/JP2011/067934 JP2011067934W WO2012020704A1 WO 2012020704 A1 WO2012020704 A1 WO 2012020704A1 JP 2011067934 W JP2011067934 W JP 2011067934W WO 2012020704 A1 WO2012020704 A1 WO 2012020704A1
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thin film
catio
white
phosphor
atomic
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PCT/JP2011/067934
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Japanese (ja)
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浩 高島
徹 京免
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独立行政法人産業技術総合研究所
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Priority claimed from JP2010188266A external-priority patent/JP5674005B2/ja
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Publication of WO2012020704A1 publication Critical patent/WO2012020704A1/fr

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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
    • C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
    • C09K11/7407—Chalcogenides
    • C09K11/7421—Chalcogenides with alkaline earth metals

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  • the present invention uses a phosphor of a perovskite oxide having excellent chemical stability and color rendering properties and a white phosphor thin film, a method for producing the same, and a phosphor and a white phosphor thin film.
  • the present invention relates to a light emitting device.
  • lighting fixtures mainly used are incandescent bulbs and fluorescent lamps.
  • a fluorescent lamp can efficiently emit ultraviolet rays of 254 nm and 185 nm by discharging mercury at a low vapor pressure. The ultraviolet light is converted into white light by the phosphor applied in the glass tube.
  • Fluorescent lamps generate much less heat than incandescent bulbs and require several percent of power to obtain the same brightness.
  • regulations have been issued in Europe to prohibit the use of harmful substances such as lead and mercury in electrical and electronic equipment related devices and devices in the future due to the RoHS directive. This is expected to limit the use of fluorescent lamps that have been used so far, and the development of new lighting devices is urgently needed.
  • Candidates for future lighting include white LEDs, organic / inorganic EL, etc., but what has been determined at this time has not been determined, and the development of white phosphors with excellent chemical stability is required. It has been.
  • Patent Documents 1 and 2 disclose fluorescence characteristics of a polycrystalline Sn perovskite oxide system.
  • Patent Document 2 shows that red, blue, and green are realized with a phosphor of a perovskite-based material using an oxide of an alkaline earth metal and zirconium as a fluorescent matrix.
  • Non-Patent Document 1 shows that fluorescence characteristics can be obtained by substituting Ca, Sr, and Ba in a polycrystalline ASnO 3 perovskite structure.
  • Non-Patent Document 2 shows that blue fluorescence can be obtained with a polycrystalline Sn-based layered perovskite structure.
  • Non-Patent Document 3 shows red fluorescence characteristics in a polycrystalline layered perovskite Sr n + 1 Ti n O 3n + 1 system.
  • Non-Patent Document 4 shows the red fluorescence characteristic of polycrystalline Pr atom substitution (CaSrBa) TiO 3 .
  • Non-Patent Document 5 shows the red fluorescence characteristic of CaTiO 3 : Pr.
  • Patent Document 3 shows the white phosphor.
  • Patent Document 3 discloses aM 1 O.bM 2 2 O 3 .cM 3 O 2 (where M 1 is one or more elements selected from the group consisting of Ba, Sr, Ca, Mg, and Zn; 2 is one or more elements selected from the group consisting of Al, Sc, Ga, Y, In, La, Gd and Lu, and M 3 is selected from the group consisting of Si, Ti, Ge, Zr, Sn and Hf.
  • An activator wherein a is 8 or more and 10 or less, b is 0.8 or more and 1.2 or less, and c is 5 or more and 7 or less.
  • the oxide of Patent Document 3 does not have a perovskite structure.
  • Non-Patent Document 6 shows that red, blue, green, and white fluorescence characteristics can be obtained by ultraviolet excitation in a tin-based perovskite structure-related oxide thin film.
  • Non-Patent Document 8 shows that red, blue, and green fluorescence appear by ultraviolet excitation by adding an appropriate rare earth element in a zirconia-based perovskite oxide thin film.
  • the present inventors have shown that red fluorescence appears by ultraviolet excitation when Pr is added in a (CaSr) TiO 3 perovskite oxide thin film (see Non-Patent Document 7).
  • Patent Document 4 an excellent red phosphor oxide epitaxial thin film formed by a pulse laser deposition method using a polycrystalline target material in which an aluminum element is added to a Pr-substituted SrTiO 3 perovskite oxide. It has been shown that the fluorescence characteristics of Specifically, it is shown that an oxide phosphor epitaxial thin film is formed on a substrate by epitaxial growth at a temperature of 600 ° C. or higher and 800 ° C. or lower by a pulse laser deposition method.
  • Patent Document 5 by the present inventors shows that red, blue, green, and white fluorescence characteristics can be obtained by ultraviolet excitation in a tin-based perovskite structure-related oxide thin film. Specifically, it is shown that an oxide phosphor epitaxial thin film is formed on a substrate by epitaxial growth at a temperature of 600 ° C. or higher and 800 ° C. or lower by a pulse laser deposition method.
  • the oxide polycrystal has been able to obtain a good phosphor in recent years, and the development of three primary colors of red, green, and blue, which are the basis of display production with the thin film, has been carried out. There was a problem that the color rendering was not sufficient.
  • EL development using thin films is indispensable, and development of oxide white phosphor epitaxial thin films is desired.
  • Non-Patent Document 6 and Patent Document 5 show a white fluorescent property in a tin-based perovskite structure-related oxide thin film, but a problem of poor color rendering because white was realized by the correlation of a plurality of sharp emission spectra. was there.
  • An object of the present invention is to solve these problems, and an object of the present invention is to provide a phosphor having a white fluorescent property with excellent color rendering property that can be used in a lighting fixture by using a perovskite oxide. To do. It is another object of the present invention to provide a manufacturing method that improves white fluorescent characteristics. It is another object of the present invention to provide a light emitting device using a perovskite oxide.
  • Another object of the present invention is to provide a phosphor epitaxial thin film having a white fluorescent property having excellent color rendering properties by ultraviolet excitation using a perovskite oxide. Moreover, it aims at providing the manufacturing method of the white fluorescent substance epitaxial thin film which improves a white fluorescence characteristic. It is another object of the present invention to provide a light emitting device using a perovskite oxide white phosphor epitaxial thin film.
  • the present invention introduces a small amount of bismuth Bi having an atomic number of 83 into CaTiO 3 , which is known as a perovskite type oxide, and has a white fluorescent property with excellent broad color rendering in a wavelength region having a center near 540 nm. Is realized.
  • the present invention realizes a phosphor thin film having the white fluorescence characteristic.
  • the present invention has the following features.
  • the present invention is a perovskite-type inorganic oxide phosphor, which is characterized in that a Bi element is added to CaTiO 3 in an amount of 0.1 atomic% to 0.4 atomic% and has white fluorescent characteristics. It can be said that the amount of Bi added is mol% with respect to CaTiO 3 .
  • the ratio of Ca to Ti is 1: 1, and the amount of Bi added is atomic% when Ca or Ti is 100%.
  • the inorganic oxide phosphor of the present invention is characterized by having an emission spectrum in the entire wavelength range of 450 to 700 nm.
  • the present invention is a method for producing an inorganic oxide phosphor, wherein Bi element is added to CaTiO 3 in an amount of 0.1 atomic% to 0.4 atomic% and fired at 900 ° C. to 1100 ° C. And Moreover, this invention relates to the light-emitting device, It has the inorganic oxide fluorescent substance of this invention, It is characterized by the above-mentioned.
  • the present invention is a white phosphor thin film of a perovskite oxide, characterized in that it is an epitaxial thin film in which Bi element is added in an amount of 0.1 atomic% to 0.4 atomic% to CaTiO 3 .
  • the epitaxial thin film can be produced by a manufacturing method described later.
  • the perovskite oxide phosphor thin film of the present invention has an emission spectrum with white fluorescence characteristics over the entire wavelength range of 450 to 700 nm.
  • the substrate used for the epitaxial thin film is preferably one of SrTiO 3 , LaAlO 3 , LaGaO 3 , MgO, and LaSrGaO 4 .
  • the present invention relates to a method for producing a white phosphor thin film of a perovskite oxide, wherein a perovskite oxide obtained by adding Bi element to CaTiO 3 in an amount of 0.1 atomic% to 0.4 atomic% is used as a target material.
  • a thin film is formed by epitaxial growth on a substrate. It can be said that the amount of Bi added is mol% with respect to CaTiO 3 .
  • the ratio of Ca to Ti is 1: 1, and the amount of Bi added is atomic% when Ca or Ti is 100%.
  • the thin film is preferably formed at a temperature of 600 ° C. or higher and 1000 ° C. or lower. Further, it is preferable to form the thin film in an oxygen pressure atmosphere of 200 mTorr or more and 1000 mTorr or less. Further, it is preferable to use a pulse laser deposition method.
  • the present invention is a light emitting device, and is characterized in that an epitaxial thin film of the present invention in which Bi element is added in an amount of 0.1 atomic% to 0.4 atomic% to CaTiO 3 is used as a phosphor thin film.
  • white fluorescence with excellent color rendering can be obtained by adding a Bi element to CaTiO 3 which is a perovskite oxide.
  • a white phosphor excellent in chemical stability can be obtained.
  • the addition amount of Bi element is 0.1 atomic% or more and 0.4 atomic% or less, a broad emission spectrum can be obtained in the entire wavelength range of 450 to 700 nm, and the emission intensity is large.
  • the emission intensity can be further improved in the wavelength region of 450 to 700 nm by firing at 900 ° C. or higher and 1100 ° C. or lower.
  • a white phosphor thin film with excellent color rendering can be obtained by adding Bi element to a CaTiO 3 thin film of a perovskite oxide.
  • a white phosphor thin film excellent in chemical stability can be obtained.
  • the addition amount of Bi element is 0.1 atomic% or more and 0.4 atomic% or less, a broad emission spectrum can be obtained in the entire wavelength range of 450 to 700 nm, and the emission intensity is large.
  • an epitaxial thin film having excellent fluorescence characteristics can be formed.
  • a perovskite oxide in which Bi element is added to CaTiO 3 by 0.1 atomic% or more and 0.4 atomic% or less can be epitaxially grown on the substrate, so that it is almost white.
  • a Bi-added CaTiO 3 thin film exhibiting fluorescence characteristics can be obtained. After the thin film is formed, excellent fluorescence characteristics can be obtained by performing a heat treatment at 900 ° C. to 1100 ° C. in the air.
  • the target material can be deposited with its stoichiometric composition by pulsed laser deposition. Further, by forming the thin film at a temperature of 600 ° C. or higher and 1000 ° C.
  • cluster growth becomes dominant, and the target material can be formed with its stoichiometric composition.
  • the target material can be formed with its stoichiometric composition.
  • a thin film in an oxygen pressure atmosphere of 200 mTorr or more and 1000 mTorr or less a broad emission spectrum can be obtained over the entire wavelength range of 450 to 700 nm.
  • Example 1 Diffuse reflection spectrum and (b) Excitation / emission spectrum of CaTiO 3 : Bi (0.2 at.%) Of Example 1 Diffuse reflection spectrum (upper) and excitation emission spectrum (lower) of CaTiO 3 : Bi added with 0, 0.1, 0.2, 0.3, 0.4, and 0.6 at.% Bi in Example 1 Luminescence intensity with respect to Bi concentration in Example 1 XRD pattern of CaTiO 3 : Bi (0.2 at.%) Baked at 900, 1000, 1100, 1200 ° C. in Example 2 Diffraction peaks on the (400), (242) and (004) planes of CaTiO 3 : Bi (0.2 at.%) Calcined at 900, 1000, 1100 and 1200 ° C. in Example 2.
  • Embodiments of the present invention will be described below.
  • the present inventors conducted the following investigation on the possibility of white fluorescence characteristics in bulk perovskite oxides. First, we searched for new perovskite phosphors under optimized synthesis conditions. CaTiO 3 , SrTiO 3 , and BaTiO 3 were used as the base material, and an element that could be expected as a luminescence center was added thereto. Table 1 shows the combinations of elements that can be expected as the base material and the emission center.
  • Luminescence was observed from a sample in which Bi was added to the combination of CaTiO 3 in Table 1. Luminescence could not be observed from other combinations.
  • CaTiO 3 uses CaCO 3 (99.99%), TiO 2 (99.99%), B 2 O 3 (99.9%), Bi 2 O 3 (99.9%), The procedure was as follows. CaCO 3 powder and TiO 2 powder were always dried in an oven at 120 ° C. to prevent moisture absorption. First, CaCO 3 and B 2 O 3 were dry-mixed and baked at 850 ° C. for 12 hours to synthesize CaB 2 O 4 serving as a flux (confirmed that there were no impurities by powder X-ray diffraction).
  • Bi 2 O 3 was dissolved in nitric acid, excess nitric acid was evaporated to bismuth nitrate, and this was dissolved in ethanol to prepare an ethanol solution of Bi (NO 3 ) 3 .
  • CaCO 3 , TiO 2 and CaB 2 O 4 were weighed at a molar ratio of 0.975: 1: 0.025 so that 1 g of CaTiO 3 : Bi was synthesized, and a Bi (NO 3 ) 3 ethanol solution was added to this.
  • Bi is added to CaTiO 3 so that it becomes 0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 mol%, and a few ml of ethanol is further added, and agate Wet mixing was performed until ethanol evaporated in the mortar.
  • This mixed powder was put into a platinum boat, heated to 1100 ° C. at 200 ° C./h, fired at that temperature for 6 h, and then cooled to room temperature to synthesize a CaTiO 3 : Bi powder sample.
  • the obtained powder was slightly agglomerated, but this was lightly pulverized to obtain a measurement sample.
  • FIG. 1 (a) and FIG. 1 (b) show diffuse reflection and excitation / emission spectra of CaTiO 3 : Bi (0.2 at.%), Respectively.
  • a broad emission was observed from 450 to 700 nm, which is a factor that appears white in the emission spectrum.
  • a peak A ′ at 335 nm and a shoulder B ′ at 365 nm were observed.
  • absorption due to the interband transition of CaTiO 3 was observed at 335 nm or less, and absorption due to the sp transition of Bi 3+ was observed near 365 nm.
  • FIG. 2 shows the diffuse reflection spectrum (upper stage) and excitation of the sample (CaTiO 3 : Bi) with Bi addition amounts of 0, 0.1, 0.2, 0.3, 0.4, and 0.6 at.%.
  • An emission spectrum (lower) is shown. Since the emission intensity of the sample to which Bi is added at 0.2 at.% Is maximum, the optimum amount of Bi added to CaTiO 3 is 0.2 at.%.
  • FIG. 3 shows the light emission intensity with respect to the Bi concentration. It can be seen that the emission intensity increases from 0 at.% To 0.2 at.% And then decreases. In addition, a sharp peak that was apparently emitted from CaTiO 3 : Pr was confirmed from the sample to which Bi was added at 0.6 at% (see FIG. 2). This is probably because Pr was mixed from the mortar during wet mixing or adhered between the cores, and mixed into the sample during firing.
  • the light emission of a phosphor using Bi is assumed to be a sp transition, and thus the light emission of the present invention is considered to be due to the Bi sp transition.
  • the wavelength of the peak A ′ in the excitation / emission spectrum shown in FIG. 1 corresponds to the band gap of CaTiO 3 , the energy of the electron-hole pair generated by the interband transition of the matrix moves to Bi and emits light. It is thought that there is.
  • the absorption near 365 nm in the reflection spectrum increases, and this absorption is considered to be due to the sp transition of Bi3 +. Therefore, the peak B ′ observed in the vicinity of 365 nm in the excitation / emission spectrum is considered to be due to the Bi3 + sp transition.
  • the amount of Bi added to CaTiO 3 is preferably 0.1 to 0.4 at.%. Further, 0.1 to 0.3 at.% Is more preferable because the emission intensity is high (FIGS. 2 and 3).
  • Example 2 firing conditions in the production of CaTiO 3 : Bi will be described.
  • the firing temperature was changed and examined.
  • a sample fired at 900, 1000, 1100, and 1200 ° C. with a firing time of 6 hours and an addition amount of Bi of 0.2 at.% was synthesized.
  • FIG. 4 shows an XRD pattern of CaTiO 3 : Bi (0.2 at.%) Fired at 900, 1000, 1100, and 1200 ° C. Only peaks attributed to CaTiO 3 were observed from the samples fired at 1100 ° C. and 1200 ° C. In addition to CaTiO 3 , peaks attributed to TiO 2 (rutile) were confirmed from the samples fired at 900 and 1000 ° C.
  • FIG. 5 shows an enlarged view of diffraction peaks on the (400), (242), and (004) planes.
  • the line width of the (242) plane in the synthesized sample is continuously narrowed from the firing temperature of 900 ° C. to 1200 ° C.
  • FIG. 6 shows a diffuse reflection spectrum (upper) and excitation / emission spectrum (lower) of CaTiO 3 : Bi (0.2 at.%) Fired at 900, 1000, 1100, and 1200 ° C.
  • the sample fired at 1200 ° C. had a marked decrease in emission intensity.
  • the shoulder B ′ near 365 nm as seen in the sample at 1100 ° C. was not seen. From the reflection spectrum, it was observed that the absorption due to the sp transition of Bi near 365 nm increased as the firing temperature was increased.
  • the firing conditions for producing the CaTiO 3 : Bi of the present invention are 900 ° C. or higher and 1100 ° C. or lower.
  • Examples 1 and 2 above examples of powder shape are shown, but the shape structure is not limited to powder, and it can be used in bulk shape, thin film shape and the like conventionally used as phosphors.
  • Example 3 an example of a thin film shape of a perovskite oxide in which Bi is added to CaTiO 3 will be described below.
  • a thin film was formed using a pulsed laser deposition method.
  • the pulse laser deposition method can form a thin film of about 500 nm in a short time (typical film formation time is 30 minutes), it is a film formation method expected to be applied to engineering. In addition, since the film can be formed in an oxygen stream, deterioration of electrical characteristics and fluorescence characteristics due to oxygen deficiency or the like can be extremely reduced during oxide thin film growth.
  • an ArF (wavelength: 193 nm) excimer laser is irradiated to a target material made of oxide in low-pressure oxygen of 1 Torr or less, and the target material is turned into plasma to form a plume, which counters the target material.
  • a superheated substrate is placed on the surface and a thin film is deposited. Cluster growth is dominant at a temperature of 1000 ° C. or lower, and the target material can be deposited with its stoichiometric composition.
  • a perovskite oxide in which Bi was added to CaTiO 3 was used as a polycrystalline target material, and the target material was irradiated with a pulse laser, and a thin film having the same composition as the target material was epitaxially grown on the substrate.
  • the polycrystalline target material is manufactured using the manufacturing method described in Examples 1 and 2. The distance between the substrate and the target was 32 mm. The laser irradiation frequency was 8 Hz, the film formation time was 30 minutes, and the film thickness was 300 nm. The laser energy is about 120 mJ.
  • a SrTiO 3 single crystal substrate polished so that the substrate surface was (001) was used as the substrate.
  • the crystal structure of SrTiO 3 is tetragonal and the lattice constant is 3.905 nm.
  • An oxide epitaxial thin film having excellent crystallinity can be grown because it has a lattice constant in the vicinity of the perovskite oxide obtained by adding Bi to CaTiO 3 of this example and has good lattice matching.
  • LaAlO 3 , LaGaO 3 , MgO, LaSrGaO 4 having good lattice matching can be used as the substrate.
  • Example 4 manufacturing conditions for manufacturing a white phosphor thin film made of CaTiO 3 to which Bi is added will be discussed below. The case where the best fluorescence characteristic was obtained and the addition amount of Bi was set to 0.2 atomic% was examined.
  • the film was formed under three conditions: the substrate temperature was 600 ° C., and the oxygen pressure during film formation was 10 mTorr, 100 mTorr, and 700 mTorr.
  • the substrate a SrTiO 3 (001) single crystal polishing substrate was used. X-ray diffraction was measured to investigate the crystal structure. As a result, it was confirmed that the (001) thin film was grown at all oxygen pressures.
  • FIG. 7 shows an X-ray diffraction pattern during growth at 600 ° C. and oxygen pressure of 700 mTorr as a typical example.
  • STO sub means SrTiO 3 substrate
  • BiCTO means Bi-added CaTiO 3 .
  • FIG. 8 shows fluorescence characteristics after film formation was performed under three conditions of a substrate temperature of 600 ° C. and an oxygen pressure of 10 mTorr, 100 mTorr, and 700 mTorr, and a heat treatment in the atmosphere at 1000 ° C. This is considered to be caused by the Bi3 + sp transition. From FIG. 8, it can be seen that a broad fluorescence characteristic cannot be obtained at an oxygen pressure of 10 mTorr or 100 mTorr, but a remarkable broad characteristic can be obtained at 700 mTorr.
  • the oxygen pressure condition is preferably 200 mTorr or more and 1000 Torr or less, and more preferably 400 mTorr or more and 1000 mTorr or less. Furthermore, the oxygen pressure conditions will be examined.
  • the pulse laser deposition method is a method in which a material having the same composition as the target material composition can be formed on the substrate by matching the distance between the substrate and the target and the mean free path of the target element particles.
  • the melting point of Bi element is 271 ° C., and a material having a low melting point temperature has a feature that it is easily scattered in plasma.
  • the mean free path of particles becomes long in low-pressure oxygen of 100 mTorr or less, only the Bi element in the Bi-added CaTiO 3 as the target material is scattered beyond the distance between the substrate and the target, and the Bi element is scattered in the thin film on the substrate. Lack. As a result, it is considered that fluorescence characteristics cannot be obtained.
  • the oxygen pressure is 700 mTorr, the mean free path and the distance between the substrate and the target match, so that the film adheres on the substrate with the composition of the target material.
  • a more preferable degree of vacuum (oxygen pressure) is 400 mTorr to 1000 mTorr.
  • a thin film can be formed at a substrate temperature of 600 ° C. or higher and 1000 ° C. or lower. This is because cluster growth is dominant at a temperature of 1000 ° C. or lower, and the target material can be deposited with its stoichiometric composition. In addition, at 500 degrees C or less, it becomes amorphous and a fluorescence characteristic is not acquired.
  • Examples 3 and 4 an example in which a film is formed by a pulse laser deposition method is shown.
  • a vapor phase growth method such as a sputtering method in addition to the pulse laser deposition method.
  • the thin film forming temperature, the oxygen pressure, and the heat treatment temperature are manufactured at the same temperature as the temperature shown in the embodiment, so that the same fluorescence characteristics as in the embodiment can be obtained.
  • the perovskite-type inorganic oxide phosphor of the present invention realizes a white fluorescent property with excellent color rendering properties and is excellent in chemical stability, and thus can be used for lighting equipment and the like.
  • the perovskite inorganic oxide phosphor thin film of the present invention realizes white fluorescent characteristics with excellent color rendering properties and is excellent in chemical stability. It can be used for luminescence devices.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un oxyde fluorescent de type perovskite présentant une excellente stabilité chimique et la propriété d'émettre une fluorescence blanche, utile dans des dispositifs électroluminescents à film fin destinés à des illuminateurs/sources lumineuses, affichages et analogue. L'invention concerne également un film fin d'un oxyde fluorescent. Par l'addition de Bi élémentaire à du CaTiO3, qui est un oxyde inorganique de type perovskite, en une quantité de 0,1-0,4%, on confère la propriété d'émettre une fluorescence blanche, l'intensité de la fluorescence étant élevée dans toute la plage de longueurs d'onde de 450-700 nm. Ce matériau fluorescent, dans de quelconques formes particulaires, en vrac et en film fin, montre ces propriétés de fluorescence blanche. L'intensité de la fluorescence peut être augmentée davantage en calcinant, à 900-1100ºC, le CaTiO3 auquel le Bi élémentaire a été ajouté en la quantité donnée. Le film fin est obtenu de préférence en utilisant une cible comprenant du CaTiO3 contenant du Bi élémentaire pour former un film fin par un procédé de dépôt par laser pulsé à une température donnée dans une atmosphère présentant une pression en oxygène donnée et par traitement par la chaleur du film fin dans l'air à une température de 900-1100ºC.
PCT/JP2011/067934 2010-08-09 2011-08-05 Matériau fluorescent d'oxyde inorganique et film fin de matériau à fluorescence blanche WO2012020704A1 (fr)

Applications Claiming Priority (4)

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JP2010-178264 2010-08-09
JP2010178264A JP5674001B2 (ja) 2010-08-09 2010-08-09 無機酸化物蛍光体及びその製造方法並びに発光装置
JP2010-188266 2010-08-25
JP2010188266A JP5674005B2 (ja) 2010-08-25 2010-08-25 白色蛍光体薄膜及びその製造方法並びに発光装置

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN102634339A (zh) * 2012-03-31 2012-08-15 昆明理工大学 一种Bi2＋激活的碱土钛酸盐红色长余辉荧光材料及其制备方法
CN114082412A (zh) * 2021-12-07 2022-02-25 温州大学 一种利用脉冲激光提高钛酸钙光催化活性的办法

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JP2008019317A (ja) * 2006-07-11 2008-01-31 National Institute Of Advanced Industrial & Technology 酸化物蛍光体エピタキシャル薄膜
JP2009155376A (ja) * 2007-12-25 2009-07-16 National Institute Of Advanced Industrial & Technology 酸化物蛍光体エピタキシャル薄膜

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JP2008019317A (ja) * 2006-07-11 2008-01-31 National Institute Of Advanced Industrial & Technology 酸化物蛍光体エピタキシャル薄膜
JP2009155376A (ja) * 2007-12-25 2009-07-16 National Institute Of Advanced Industrial & Technology 酸化物蛍光体エピタキシャル薄膜

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TANG WANJUN, CHEN DONGHUA: "Photoluminescence properties Pr3+ and Bi3+-codoped CaTiO3 phosphor prepared by a peroxide-based route", MATERIALS RESEARCH BULLETIN, vol. 44, no. 4, 2 April 2009 (2009-04-02), pages 836 - 839, XP025947510 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102634339A (zh) * 2012-03-31 2012-08-15 昆明理工大学 一种Bi2＋激活的碱土钛酸盐红色长余辉荧光材料及其制备方法
CN114082412A (zh) * 2021-12-07 2022-02-25 温州大学 一种利用脉冲激光提高钛酸钙光催化活性的办法
CN114082412B (zh) * 2021-12-07 2023-07-21 温州大学 一种利用脉冲激光提高钛酸钙光催化活性的办法

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