WO2006131795A1 - Compositions pour decalage spectral - Google Patents

Compositions pour decalage spectral Download PDF

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Publication number
WO2006131795A1
WO2006131795A1 PCT/IB2006/001284 IB2006001284W WO2006131795A1 WO 2006131795 A1 WO2006131795 A1 WO 2006131795A1 IB 2006001284 W IB2006001284 W IB 2006001284W WO 2006131795 A1 WO2006131795 A1 WO 2006131795A1
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WIPO (PCT)
Prior art keywords
phosphors
phosphor compositions
phosphor
further characterized
formula
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PCT/IB2006/001284
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English (en)
Inventor
Vladimir Semenovich Abramov
Naum Petrovich Soshin
Alexander Valerievich Shishov
Nicolay Valentinovich Scherbakov
Valentin Nikolaevich Scherbakov
Andrey Nikolaevich Turkin
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Acol Technologies Sa
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Publication of WO2006131795A1 publication Critical patent/WO2006131795A1/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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77342—Silicates
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77344—Aluminosilicates
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/77924—Aluminosilicates

Definitions

  • the following inventions disclosure is generally concerned with compositions for shifting wavelengths of light and specifically concerned with phosphor materials suitable for use with light emitting diodes and light emitting diodes packaging technologies.
  • a high brightness blue LED is combined with a wavelength shifting phosphor. This special phosphor is charged by blue light emitted at the semiconductor.
  • the phosphor When stimulated, the phosphor re-emits light, albeit with less energy (longer wavelength) than the stimulating or pumping light. Phosphors which are stimulated by blue light and emit yellow light have been used to form 'white' LEDs.
  • YAG based phosphors have become a leading high performance class of wavelength shifting phosphor used with blue and UV LEDs.
  • U.S. patent 5,998,925 describes systems where a YAG based phosphor is used to convert blue light emitted from a nitride semiconductor into yellow light. Some of the blue light passes without being shift and together the emission spectrum is characterized as broadband and appears as a 'cool white ' ' color.
  • Other recent and related U.S. Patents employing wavelength shifting phosphors which further define the art include: 6,603,258; 6,657,379; 6,686,691; 6,717,353;
  • a luminophore based upon alkalijie-earth orthosilicates is activated with a bivalent Europium.
  • the output spectra are further enhanced by way of blends including alkaline- earth aluminates activated by Europium and Manganese and further by red emitting phosphor to promote warmer color temperatures.
  • Maeda et al teach semiconductor light emitting devices and associated production methods where yellow and yellowish phosphor particles are made as a silicate phosphor. Appropriately distributed in a resin, the phosphor converts light and promotes an 'excellent white light'.
  • a Strontium silicate based phosphor is disclosed in PCT publication numbered: WO 2004/067677 published on 12 August 2004. These inventions are applied to a long wavelength ultraviolet LED or an active luminous LCD to enable improvements in color purity and enhance luminous efficiency.
  • Phosphors of these inventions are particularly well suited for the specific task of forming a 'white' or broadband spectral output from a high brightness blue LED via wavelength shifting. That is, these phosphors are readily and efficiently pumped by wavelengths available in most common blue LEDs, and further, they re-emit light with a highly desirable spectrum to produce a broadband white output. These compositions have high quantum efficiency and are inexpensive to manufacture.
  • Gallium Nitride LEDs are a very special new class of LEDs which produce a blue light output. Lately, these have been manufactured (by Nichia) among others in very high brightness configurations. Blue light has higher energy than all other visible colors.
  • This high energy light is useful for 'pumping' or 'exciting' phosphors which then re-emit in other colors.
  • the present inventions have been specifically prepared and designed with a view toward these gallium nitride LED semiconductors as a pump source. These phosphors are 'tuned' whereby they are efficiently responsive to blue light. This has the result of improving the quantum efficiency of the system. Blue light which falls incident upon the phosphor crystals is converted to other colors of the phosphor output spectrum with low heat loss mechanisms.
  • Fig. 1 illustrates the radiation spectrum of orthosilicate photo luminescent phosphor Sri. 6 Bao. 29 Cao. t Euo.o 1 SiO 4 .
  • Fig 2a and Fig 2b shows a radiation/excitation spectra respectively for prior art
  • Fig. 3 represents photo luminescent phosphor radiation spectrum Sro.39Bao.6Euo.o1 SiO 4 .
  • wavelength shifting phosphor compositions and methods of manufacturing same are provided. It will be appreciated that each of the embodiments described include both a composition and method and that the compostion and method of one preferred embodiment may be different than the composition and method of another embodiment.
  • phosphors are high performance phosphors which are application specific. Namely, the phosphors are best used in conjunction with blue light emitting gallium nitride semiconductor diodes. Light emitted by the semiconductor is narrowband and typically in the blue spectral region. These phosphors are tuned whereby they 'pumped' by this blue light. That is to say, blue light is readily absorbed by these phosphors and re-emitted at longer wavelengths. More particularly, wavelenths in the green, yellow, amber, and red regions of the visible spectrum.
  • blue light from the semiconductor mixes with re-emitted light from the phosphor to produce a wideband spectral output or 'white' light device.
  • Phosphors not properly tuned to the input energy i.e. the blue light of gallium nitride semiconductors, do not perform so well.
  • phosphors which re-emit light in other spectral regions will not produce the highest quality of white light (for example a white having undesirable color temperature).
  • these phosphors have further advantageous qualities. They have very high quantum efficiency. That is, a high ratio of absorbed photons cause re-emission and a high optical output.
  • these phosphor compositions are comprised of special elements which are readily available and inexpensive. The resulting phosphors are amenable to common manufacturing processes. They are further durable against heat degradation to give a long life.
  • This new family of phosphors is primarily characterized by the stoichiometric expression
  • Me +2 includes at least one of the group 2A elements. In most cases, this means either from the group including: Mg; Ca; Sr; and Ba.
  • the family is further defined via the expression where x is equal to or between 0 and 3; y is either 0 or 2; and z is equal to or between 0 and 3.
  • TR +2 is known as the 'activator' and is selected from either of the elements in the group: Eu; Sm; and Yb; or combinations thereof.
  • these phosphors are comprised of crystals which take special form.
  • This family of phosphors may include monoclinic and rhombic forms and belong to hexagonal and cubic syngony. Thus a major difference between this family of phosphors and those known relates to crystal structure.
  • Monoclinic rhombic crystal having hexagonal syntony provides narrower band luminescent.
  • An approximate half width of ⁇ 6Q nm of activating rare-earth ions with oxidation level +2 (Eu +2 and/or Sm +2 ) can be expected. This relatively narrow half width improves coupling between the phosphors' pump energies and emission energies.
  • This family of phosphors has a high pump efficiency (absorption) at about between 380 to 500 nm.
  • Phosphors in the family presented have re-emission spectra characterized as lying in the range about between 500 and 620. In addition, this is highly tunable.
  • the phosphor composition and form By adjusting the phosphor composition and form, one can produce results which vary with regard to how it re-emits light at various parts of the long wave end of the visible spectrum.
  • these phosphors are tuned to maximize coupling between the absorption spectrum of the phosphor and the emission spectrum of the semiconductor chip, and further the output spectrum of the phosphor with respect to desired color temperature.
  • the anion sub lattice of this family of phosphors is comprised of oxides such as
  • the cation sublattice includes such elements as Mg; Ca; Sr; and Ba, or combinations thereof.
  • the cation sublatice may include in definite part (from .001 up to .2 atom shares) activating dopes in the form of Eu; Sm or Yb.
  • This family of phosphors doesn't include rare earth elements commonly found in phosphors commonly used as wavelength shifting medium for semiconductor chips.
  • Phosphors belonging to this family do not include: Y 2 O 3 , Gd 2 O 3 , Ce 2 O 3 , Ga 2 O 3 , Tb 2 O 3 , Sc 2 O 3 , In 2 O 3 , Yb 2 O 3 , Pr 2 O 3 .
  • Phosphors used for the conversion of shorter wavelengths to longer wavelengths, particularly those used to convert blue emitting semiconductors into 'white' LEDs are generally based upon these rare earth oxides. Reference to the art will confirm this.
  • Nichia's popular cerium activated YAG fluorescent phosphor contains: oxides of Y, Lu, SC, La, Gd and Sm.
  • phosphors of this family are recombination mechanisms of luminescence excitation.
  • Phosphors of the art commonly use Ce " containing garnets where the excitation is made directly to luminescence center.
  • the phosphor family described here can be defined as phosphorescent silicate materials, activated by bivalent ions.
  • this phosphor family may be characterized by all its main properties:
  • the chromaticity and their radiance spectrum depend on the ratio between cations Mg 5 Ca, Sr, Ba and activating ions Eu +2 , Sm +2 , Yb +3 , which homovalently replace the main cations in a cation sublattice.
  • the changing of ratio between Mg, Ca, Sr to the favor of a small dimension cation (crystal structure) leads to a shift of radiance maximum towards shorter wavelengths, whereas, more or less concentration of the main activator Eu +2 , Sm +2 and/or Yb +2 provides for the changing of the intensiveness of the main spectrum maximum.
  • Table 1 demonstrates summary data on the described phosphor family.
  • n ph ⁇ 1.72.
  • dialurninium-disilicates Mg, Ca, Sr, Ba
  • Al 2 Si 3 O 121 -Eu +2 composition are the most efficient.
  • the additional activation Eu +2 materials by Yb + -ion is accompanied by reducing major activator duration persistence.
  • the maximum concentration of the input activators Eu +2 +Su +2 +Yb +2 does not exceed 0.2 atomic shares though the optimal concentration is within the interval from 0.02 up to 0.06 atomic shares.
  • the optimal quantity of the input Yb +2 equals to 0,001 ⁇ 0.003.
  • the ratio between Mg:Ca:Sr:Ba allows to control the radiation position of the major spectrum maximum and maximum at excitation spectrum of phosphor.
  • Si ⁇ 2 -anions quantity is low, i.e. for mono- and orthosilicates ?
  • Ba +2 large-dimension cation shifts radiation spectrum Eu +2 to 50 ⁇ 70 nm during replacing from 0.1 up to 0.4 atomic shares of the major cations (Mg, Ca, or Sr).
  • compositions of matter but rather, explicitely include methods, i,e. the methods of forming these compositions, in addition to those unique compositions per se.
  • methods of these inventions include forming a wavelength shifting phosphor characterized by the expression: (Me +2 ) x AIySi 2 O ( 2 ⁇ + 3 y + 4 z )/2 : (TR +2 ) q , where Me +2 is a group 2A element; TR +2 , is a lanthanoid; x is either 0, 1-q, 2-q, or 3-q; y is either 0, 2; z is either 0, 1, 2, 3; and q is 0.001 - .2 atom proportion, the methods comprising the steps: mixing together ingredients; adding an activating additive; added by halogenated mineralizators; annealing the mixture in a stepped temperature scheme; introducing the mixture to reducing atmosphere; performing a final annealing step at elevated temperature; cooling resulting product in nitrogen atmosphere at temperature lower than 100 0 C; wash product in solution of weak hydrochloric acid; drying to remove excess moisture; and sifting through a sieve.
  • these methods include those where: oxides, carbonates and hydrocarbons are mixed; at least one of: Eu 2 O 3 , is Sm 2 O 3 and Yb2 ⁇ 3 is added; halogenated mineralizators are at least one of either: MgF 2 , CaF 2 , SrF 2 , MgCl 2 and BaCIa; the stepped temperature scheme includes: T is about
  • T is about 1250 for three hours; the reducing atmosphere consists of about 5% H 2 + 95% N 2 ; the final annealing is at T is between about 1200 - 1350°C for approximately 3 hours; and the final product is filtered for size through a sieve of 400 to 500 mesh.
  • the carbonates mixture containing of CaCO 3 , SrCO 3 , BaCO 3 and hydroxycarbon MgCO 3 -Mg(OH) 2 is added to the oxides.
  • Activating additives of europium, samarium and ytterbium are added in the form OfEu 2 O 3 , Sm 2 O 3 and Yb 2 O 3 oxides.
  • This mixture is added by halogenated mineralizators such as MgF 2 , CaF ⁇ , SrF 2 , MgCl 2 and BaCl 2 which total mass does not exceed 10% of the used oxides mass.
  • the resulting product is cooled at nitrogen atmosphere at temperature lower than 100 0 C, then is washed by the solution of weak hydrochloric acid, is dried and sifted through a sieve of 400 or 500 mesh.
  • components including:
  • MgCl 2 - 6g BaC ⁇ r 2H 2 O - 10g can be mixed in a tumbling mill with intermediate sifting of the mixture through the 100 microns vibrating sieve until homogeneity.
  • the mixture is loaded into alundum capsule (1000 ml) then thoroughly rammed and put into the furnace with the controlled temperature.
  • the mass is cooled to 100 0 C, washed by weak (1:10) hydrochloric acid, dried at T - 12O 0 C till dust and then sifted.
  • the average grains diameter of the received mass equals 10 microns and is used for making the suspension in silicone ash (the polymer molecular mass «6000 carbon units).
  • the components including:
  • Example 3 0.4M MgCO 3 2.4M SrCO 3 0.1M BaCO 3 0.1M CaCO 3 0.01M Eu 2 O 3
  • 0.1M MgF 2 should be mixed in a tumbling mill, sifted through vibrating sieve and loaded into alundum capsule (1000ml).
  • the product is cooled in nitrogen environment, washed by weak hydrochloric acid, dried and sifted.
  • Example 4 The mixture consisting of:
  • Phosphor with the composition (Mg 5 Ca 5 Sr, Ba) 3 Si 2 O 7 relates to monoclinic syngony (mineral-rankinite) and radiates in a blue-yellow spectrum sub-band with quantum yield equal to 0,72.
  • Example 5 The components including:
  • Phosphor powder should be washed by acetone and sifted through the 400 mesh sieve.
  • Phosphor samples are cooled in nitrogen atmosphere, washed by 1 : 3 hydrochloric acid, dried and sifted.
  • Sample A relates to monoclinic syngony, emits in green and yellow spectrum area with quantum yield equal to 0.57.
  • Sample B has a monoclinic lattice and emits in greenish and yellow spectrum subband with quantum yield equal to 0.58. Examples 9-11
  • the first composition group relates to monoclinic syngony and emits in bluish-green and green spectrum sub-band with quantum yield equal to 0,61.
  • the second sample group represents the same monoclinic structure and intensely emits with quantum yield equal to 0.65.
  • the composition contains only Al +3 ion out of the whole chemical composition of a typical garnet despite the cubic syngony the standard yttrium-garnet phosphor Y 3 ⁇ (Gd 5 Ce) x (Al 5 Ga)SO 12 belongs.
  • combinations include: semiconductor chip emitting between about 350nm and 500nm; and a phosphor defined by the expression: (Me +2 ) x Al y Si z 0(2 ⁇ +3y +4z)/2 : (TR +2 )q, where Me +2 is a group 2A element; TR +2 is a lanthanoid; x is either 0, 1-q, 2-q, or 3-q; y is either 0, 2; z is either 0, 1, 2, 3; and q is 0.001 - .2 atom proportion. More specifically a gallium nitride diode having heteroj unctions of Gai. p ⁇ n p N (p>0,l).
  • the semiconductor is in relation with the phosphor by way of a transparent organic binder which holds the phosphor grains distributed therein.

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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 des phosphores destinés à être utilisés avec des diodes électroluminescentes bleues de haute intensité, ainsi que leurs procédés de fabrication. Ces phosphores sont tout à fait appropriés à la production spécifique d'une sortie spectrale' blanche' ou à large bande d'une diode électroluminescente bleue de grande luminosité par décalage spectral. Ces phosphores ont été spécifiquement préparés et conçus dans le but de les utiliser avec des semi-conducteurs de diodes électroluminescentes de nitrure de gallium. Ils sont 'accordés' de façon à réagir efficacement à la lumière bleue. Ceci permet d'améliorer le rendement quantique du système. Dans de meilleures versions de ces phosphores, l'utilisation des composants les plus chers des compositions de phosphores typiques de la technique antérieure a été abandonnée. Les phosphores de cette invention ont été conçus et disposés de façon à fonctionner pleinement sans qu'il soit besoin d'utiliser des produits chimiques extrêmement chers comme c'est le cas dans les systèmes de la technique antérieure. La production de ces phosphores s'avère ainsi moins chère, et ceux-ci sont mieux appropriés pour être utilisés dans des applications telles que l'éclairage secondaire.
PCT/IB2006/001284 2005-06-06 2006-05-17 Compositions pour decalage spectral WO2006131795A1 (fr)

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US11/144,454 2005-06-06

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009072539A1 (fr) * 2007-12-07 2009-06-11 Kabushiki Kaisha Toshiba Phosphore et dispositif électroluminescent del l'utilisant
KR20110115716A (ko) * 2010-04-16 2011-10-24 서울반도체 주식회사 스트론튬 옥시오소실리케이트 유형의 형광체를 갖는 발광 장치
WO2011078509A3 (fr) * 2009-12-21 2011-11-10 Seoul Semiconductor Co., Ltd. Dispositif émettant de la lumière ayant des luminophores de type oxyorthosilicate de strontium
US8173042B2 (en) 2009-12-21 2012-05-08 Seoul Semiconductor Co., Ltd. Strontium oxyorthosilicate phosphors having improved stability under a radiation load and resistance to atmospheric humidity
CN106281307A (zh) * 2016-07-18 2017-01-04 天津泰达环保有限公司 一种含稀土的柔性壳聚糖发光薄膜及其制备方法
WO2018137310A1 (fr) * 2017-01-25 2018-08-02 广明源光科技股份有限公司 Poudre fluorescente pour source lumineuse à del ayant un effet de répulsion d'insectes, source lumineuse à del, lampe de répulsion d'insectes et dispositif de répulsion d'insectes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1205298A (en) * 1967-10-26 1970-09-16 Philips Electronic Associated Luminescent materials
US4236078A (en) * 1978-07-12 1980-11-25 Fuji Photo Film Co., Ltd. Method and apparatus for recording and reproducing a radiation image
US6621211B1 (en) * 2000-05-15 2003-09-16 General Electric Company White light emitting phosphor blends for LED devices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1205298A (en) * 1967-10-26 1970-09-16 Philips Electronic Associated Luminescent materials
US4236078A (en) * 1978-07-12 1980-11-25 Fuji Photo Film Co., Ltd. Method and apparatus for recording and reproducing a radiation image
US4236078B1 (fr) * 1978-07-12 1989-01-03
US6621211B1 (en) * 2000-05-15 2003-09-16 General Electric Company White light emitting phosphor blends for LED devices

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9169436B2 (en) 2007-12-07 2015-10-27 Kabushiki Kaisha Toshiba Phosphor and LED light emitting device using the same
US8487330B2 (en) 2007-12-07 2013-07-16 Kabushiki Kaisha Toshiba Phosphor and LED light-emitting device using the same
US9660149B2 (en) 2007-12-07 2017-05-23 Kabushiki Kaisha Toshiba Phosphor and LED light emitting device using the same
WO2009072539A1 (fr) * 2007-12-07 2009-06-11 Kabushiki Kaisha Toshiba Phosphore et dispositif électroluminescent del l'utilisant
JP5330263B2 (ja) * 2007-12-07 2013-10-30 株式会社東芝 蛍光体およびそれを用いたｌｅｄ発光装置
JP2013515130A (ja) * 2009-12-21 2013-05-02 ソウル セミコンダクター カンパニー リミテッド ストロンチウムオキシオルトシリケート型の蛍光体を有する発光装置
US8440106B2 (en) 2009-12-21 2013-05-14 Seoul Semiconductor Co., Ltd. Strontium oxyorthosilicate phosphors having improved stability under a radiation load and resistance to atmospheric humidity
US8173042B2 (en) 2009-12-21 2012-05-08 Seoul Semiconductor Co., Ltd. Strontium oxyorthosilicate phosphors having improved stability under a radiation load and resistance to atmospheric humidity
US8963173B2 (en) 2009-12-21 2015-02-24 Seoul Semiconductor Co., Ltd. Light emitting device having strontium oxyorthosilicate type phosphors
WO2011078509A3 (fr) * 2009-12-21 2011-11-10 Seoul Semiconductor Co., Ltd. Dispositif émettant de la lumière ayant des luminophores de type oxyorthosilicate de strontium
KR20110115716A (ko) * 2010-04-16 2011-10-24 서울반도체 주식회사 스트론튬 옥시오소실리케이트 유형의 형광체를 갖는 발광 장치
KR101670947B1 (ko) * 2010-04-16 2016-11-01 서울반도체 주식회사 스트론튬 옥시오소실리케이트 유형의 형광체를 갖는 발광 장치
CN106281307A (zh) * 2016-07-18 2017-01-04 天津泰达环保有限公司 一种含稀土的柔性壳聚糖发光薄膜及其制备方法
WO2018137310A1 (fr) * 2017-01-25 2018-08-02 广明源光科技股份有限公司 Poudre fluorescente pour source lumineuse à del ayant un effet de répulsion d'insectes, source lumineuse à del, lampe de répulsion d'insectes et dispositif de répulsion d'insectes

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