KR20160113471A - Phosphor, Method of fabricating the same, and Light Emitting Device of using the same - Google Patents
Phosphor, Method of fabricating the same, and Light Emitting Device of using the same Download PDFInfo
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- KR20160113471A KR20160113471A KR1020150039092A KR20150039092A KR20160113471A KR 20160113471 A KR20160113471 A KR 20160113471A KR 1020150039092 A KR1020150039092 A KR 1020150039092A KR 20150039092 A KR20150039092 A KR 20150039092A KR 20160113471 A KR20160113471 A KR 20160113471A
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- fluoride
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 72
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 48
- 239000011247 coating layer Substances 0.000 claims abstract description 41
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims description 21
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 20
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 20
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000005642 Oleic acid Substances 0.000 claims description 20
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 125000001165 hydrophobic group Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000011368 organic material Substances 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 4
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 4
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 4
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 230000008859 change Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
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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
- C09K11/0827—Halogenides
- C09K11/0833—Halogenides with alkali or alkaline earth metals
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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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
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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
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- Organic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
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Abstract
Description
The present invention relates to a phosphor and a light emitting device using the same, and more particularly, to a fluoride-based fluorescent material having a coating layer, a method for producing the same, and a light emitting device using the formed fluoride-based fluorescent material.
Phosphors can be used in vacuum fluorescent display (VFD), electroluminescent display (FED), plasma display panel (PDP), cathode ray tube (CRT) or white light emitting diode (WLED), and the like as vacuum ultraviolet ray, ultraviolet ray, electron beam, near ultraviolet ray and blue light. It is a substance that receives energy from an excitation source having energy and emits light of a specific wavelength band. Among these applications, researches on light emitting diodes having high efficiency and environment-friendly advantages compared to the existing methods are being actively pursued along with global interest in environment such as recent global energy crisis and global warming.
In order for a light emitting diode having excellent advantages to be used as a solid light source to replace an existing light source, it is most important to realize high-quality white light, and a phosphor having good characteristics is required in this regard. There are three main ways to realize white light using light emitting diodes.
First, a white light emitting diode is implemented by combining three light emitting diodes emitting red, green, and blue light. This method is disadvantageous in that the operating voltage is uneven for each chip and the output of the chip is changed according to the ambient temperature and the color coordinates are changed and the price is high because of excellent color rendering due to wide wavelength spectrum emitted.
Second, white light is realized by mixing near-UV LEDs with blue, green or yellow and red phosphors as light sources. This method is very similar to the method of embodying a fluorescent lamp with ultraviolet rays. It has a very wide wavelength spectrum such as an incandescent lamp, has excellent color stability, and has an advantage in that it can easily control correlated color temperature and color rendering index. It is being studied for the implementation of white LED for illumination. However, many improvements are still needed in terms of efficiency.
Third, a blue LED is used as a light source to excite a yellow phosphor to realize a white color. This method has a simple structure of one chip and two terminals, so it can reduce manufacturing cost and has excellent luminous efficiency. However, it has a limitation that it is difficult to apply it as a high quality solid light source because of low color rendering index due to insufficient light emission in the red region.
In order to solve this problem, CaAlSiN 3 : Eu 2+ , (X.Piao, et al., Chem. Mater., 19, 4592, 2007), K 2 SiF 6 : Mn 4+ Red phosphors are mainly used, such as red phosphors, red phosphor, red phosphor, and red phosphor.
In particular, the CaAlSiN 3 : Eu 2+ red phosphor exhibits excellent thermal and moisture resistance characteristics in the construction of a white light emitting device and is continuously used. However, its emission wavelength is located at a long wavelength and Eu 2+ Has a luminescence property with a wide half width and adversely affects the efficiency and color purity of the white light emitting device.
On the other hand, the K 2 SiO 6 : Mn 4+ phosphor has an emission wavelength of about 620 nm and a very narrow emission half band width, so that it can be expected to have an excellent color characteristic as compared with the CaAlSiN 3 : Eu 2+ red phosphor described above . However, since the K 2 SiO 6 : Mn 4+ phosphor contains fluorine in the matrix, the moisture stability (moisture resistance) is very weak, and thus, the white color and the stability of the white light emitting device are very badly affected.
In the white light emitting element, when sealing the phosphor with the light emitting diode chip, a moisture permeable resin such as epoxy resin or silicone resin is generally used, and the phosphor is required to have moisture resistance for a long period of time. However, since the K 2 SiO 6 : Mn 4+ phosphor has poor moisture resistance and is sealed with a moisture-permeable resin, the emission intensity of the white light-emitting device is greatly reduced due to the deterioration of the phosphor after a certain period of time, .
In order to solve the above problems, the present invention provides a fluoride-based phosphor having improved moisture resistance, a method of manufacturing the same, and a light emitting device using the same.
According to an aspect of the present invention, there is provided a fluoride fluorescent body comprising: And a hydrophobic coating layer formed on the surface of the fluoride fluorescent body.
[Chemical Formula 1]
A 2 BF 6 : Mn 4+
Wherein A is at least one element selected from the group consisting of Li, Na, K, Rb and Cs as a monovalent metal cation, B is a tetravalent cation and is selected from the group consisting of Ge, Si, Sn and Ti At least one element.
The above object of the present invention can also be achieved by a method for manufacturing a fluorescent lamp, comprising the steps of: mixing a fluoride fluorescent body with an organic solvent; Introducing an organic substance having a hydrophobic group into an organic solvent into which the fluoride fluorescent body is incorporated; And bonding the organic material having the hydrophobic group to the fluoride fluorescent body to form a hydrophobic coating layer.
The above object of the present invention is also achieved by a light emitting device having a phosphor disposed on a light emitting diode emitting blue light and absorbing the blue light and emitting light of a specific wavelength band, A fluoride fluorescent body; And a hydrophobic coating layer formed on the surface of the fluoride fluorescent body.
(2)
A 2 BF 6 : Mn 4+
Wherein A is at least one element selected from the group consisting of Li, Na, K, Rb and Cs as a monovalent metal cation, B is a tetravalent cation and is selected from the group consisting of Ge, Si, Sn and Ti At least one element.
According to the present invention, a hydrophobic coating layer is formed on the surface of the fluoride fluorescent body. The moisture-absorbing property of the fluoride-based fluorescent material is remarkably improved by the formation of the hydrophobic coating layer. This is because the hydrophobic coating layer blocks the degradation of the properties of the fluorescent body due to moisture, thereby forming the fluoride-based fluorescent substance having improved moisture resistance. Further, the light-emitting element formed using the same can ensure excellent moisture resistance.
1 is a flowchart illustrating a method of manufacturing a fluoride-based fluorescent material according to a preferred embodiment of the present invention.
2 is an XRD graph of a phosphor prepared according to a preferred embodiment of the present invention.
3 is an image of a phosphor prepared according to a preferred embodiment of the present invention.
4 is a PL graph of a phosphor prepared according to a preferred embodiment of the present invention.
5 is a FT-IR characteristic graph of a phosphor prepared according to a preferred embodiment of the present invention.
FIG. 6 is a graph showing the PL characteristic of the phosphor prepared according to the preferred embodiment of the present invention.
7 is a PL graph showing the characteristics of the phosphor formed by Production Example 2 of the present invention.
FIG. 8 is a graph showing the characteristics of phosphors manufactured according to a preferred embodiment of the present invention.
The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing.
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example
The phosphor according to this embodiment is intended to solve the problem of moisture resistance of the fluoride-based fluorescent material. The reason why the moisture resistance of the fluoride-based fluorescent material is deteriorated is due to fluorine contained in the matrix of the fluorescent material, and thus the hydrolysis reaction by water is likely to occur on the surface of the fluorescent material, thereby changing the phosphor composition and crystal structure. This is because elution reaction and oxidation number change of manganese ions as active ions occur.
In the phosphor according to the present embodiment, an organic material having hydrophobic properties is surface-treated on the fluorescent body. Fluoride-based phosphors are stable to moisture.
The fluorescent substance body according to the present embodiment has the following structure (1).
[Chemical Formula 1]
A 2 BF 6 : Mn 4+
Wherein A is at least one element selected from the group consisting of Li, Na, K, Rb and Cs as a monovalent metal cation, B is a tetravalent cation and is selected from the group consisting of Ge, Si, Sn and Ti At least one element.
In the organic substance having a hydrophobic group bonded to the fluorescent body of Formula 1, the hydrophobic group may be a cyano group, a nitro group, an alkyl group having a carbon number of 1 to 18, a haloalkyl group having a carbon number of 1 to 18, a cycloalkyl group having a carbon number of 3 to 8, An alkoxy group having 1 to 8 carbon atoms, an alkylcarbonyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 109 carbon atoms, An alkyl group or an arylcarbonyl group having 6 to 10 carbon atoms.
There is no particular limitation on the organic substance having a hydrophobic group, and any organic substance having any hydrophobic group may be used as long as it is a substance capable of binding to the fluorescent substance body of Formula 1 and forming a coating. For example, the organic material having a hydrophobic group may be myristic acid, trioctylphosphine, trioctylphosphine oxide, cellulose triacetate, 1-octadecene, palmitic acid or oleic acid.
In addition, when the hydrophobic coating layer composed of an organic material having a hydrophobic group is discontinuously formed in a particle shape on the fluorescent body, moisture can not be effectively blocked under a moisture-resistant environment. Therefore, it is preferable that the hydrophobic coating layer is formed as a continuous film on the surface of the fluorescent body. Of course, in some surfaces, the hydrophobic covering layer may expose the surface of the fluorescent body, but it is preferable that the hydrophobic covering layer shields a substantial part of the surface of the fluorescent body.
1 is a flowchart illustrating a method of manufacturing a fluoride-based fluorescent material according to a preferred embodiment of the present invention.
Referring to FIG. 1, a fluoride fluorescent body is incorporated into an organic solvent. The fluoride fluorescent body is defined in the above formula (1). For example, the K 2 SiF 6 : Mn 4+ fluorescent body is incorporated into the organic solvent. The organic solvent is preferably a nonpolar organic solvent. For example, ethanol or the like may be used as the alcohol.
Subsequently, an organic substance having a hydrophobic group is mixed and dispersed in a solution in which the fluoride fluorescent body and the organic solvent are mixed. Organic materials having hydrophobic groups that can be used can be selected variously, and oleic acid can be used. However, it is required that a solution in which organic matter having a hydrophobic group is mixed does not contain water.
Subsequently, an organic material having a hydrophobic group is bonded to the fluoride fluorescent body to form a hydrophobic coating layer. The formation of the hydrophobic coating layer can be carried out through various methods. For example, a mixing and heating method for a mixed solution of an organic material having a hydrophilic group can be used. In this method, the hydrophobic coating layer can be formed by mixing the solvent thermally-synthesized method, the magnetic stirrer stirring method using a temperature elevating process, the ultrasonic dispersion and heating, the mixing and heating using a rotary mixer, the reflux synthesis method, or a combination thereof.
Particularly, in this embodiment, it is required that the organic solvent used in the solvent thermo-synthetic method does not contain water. In the case of forming a hydrophobic coating layer on the fluorescent body by using a solvent thermo-synthetic method using the fluorescent body of formula (1) and the water-soluble organic substance, hydrolysis reaction by water does not occur, fluorescence properties of the fluorescent substance are not deteriorated, Lt; / RTI > In addition, it is expected that the emission intensity can be increased by improving the crystallinity of the phosphor in a high-temperature and high-pressure environment.
Production Example 1
0.7 g of K 2 SiF 6 : Mn 4+ fluorescence body was mixed with 25 ml of ethanol, 3 ml of oleic acid was further mixed, and the mixture was stirred at room temperature for 30 minutes to homogeneously mix the hydrophobic oleic acid with ethanol.
Subsequently, the mixed solution is transferred to the reactor to perform the solvent thermo-synthetic method, and then the reaction is maintained for 6 hours in an oven maintained at 140 ° C. Then, when the reactor reaches room temperature, the phosphor and ethanol are separated from the mixed solution. The separated phosphor is washed with ethanol, and the washed phosphor powder is dried in an oven maintained at 70 ° C. for 12 hours.
2 is an XRD graph of a phosphor prepared according to a preferred embodiment of the present invention.
Referring to FIG. 2, an X-ray diffractometer (Philips X'Pert diffractometer) was used to analyze the crystal structure of the mold and sieve, and K 2 SiF 6 : Mn 4+ fluorescence The crystal structure of the K 2 SiF 6 : Mn 4+ phosphor in which the main body and the hydrophobic coating layer are formed is compared. The K 2 SiF 6 : Mn 4+ phosphor maintains the same crystal structure as that of the K 2 SiF 6 : Mn 4+ fluorescent body even when a hydrophobic coating layer is formed by the solvent thermo-synthetic method, and an unnecessary secondary phase is formed or impurities Is not formed.
3 is an image of a phosphor prepared according to a preferred embodiment of the present invention.
Referring to FIG. 3, images of three phosphors are shown. The first image shows the K 2 SiF 6 : Mn 4+ particles before the addition to the ethanol to form the hydrophobic coating layer, the second image shows the K 2 SiF 6 : Mn 4+ particles, and the third image shows K 2 SiF 6 : Mn 4+ particles which are fed into ethanol and loaded with oleic acid to form a hydrophobic coating layer.
The three images are SEM (FEOSEM, Hitachi S-4700) images, indicating no image change on the crystal structure. That is, even if the hydrophobic coating layer is formed on the fluorescent substance body by using the solvent thermo-synthetic method or the like, the change in crystallinity or appearance does not occur in the fluorescent substance itself.
4 is a PL graph of a phosphor prepared according to a preferred embodiment of the present invention.
Referring to FIG. 4, graph A shows the characteristics of a K 2 SiF 6 : Mn 4+ phosphor in which hydrophobic oleic acid was formed as a hydrophobic coating layer according to the preparation example. In graph B, the manufacturing process was applied for solvent thermolysis, The characteristics of the K 2 SiF 6 : Mn 4+ phosphor in which oleic acid is not added and the graph C is a characteristic graph of the K 2 SiF 6 : Mn 4+ phosphor before the solvent thermal synthesis is performed. To obtain the graph, the excitation wavelength? Ex for the three samples is set to 450 nm.
It is confirmed that the crystallinity of the phosphor is slightly increased by the heat applied for forming the hydrophobic coating layer through the hydrophobic oleic acid, thereby increasing the emission intensity.
5 is a FT-IR characteristic graph of a phosphor prepared according to a preferred embodiment of the present invention.
Referring to FIG. 5, graph A shows the characteristics of the K 2 SiF 6 : Mn 4+ phosphor in which hydrophobic oleic acid is not added, while the manufacturing process is applied for solvent thermal synthesis. Of K 2 SiF 6 : Mn 4+ phosphor. Graph C is a characteristic of a K 2 SiF 6 : Mn 4+ phosphor in which hydrophobic oleic acid was formed as a hydrophobic coating layer according to the above production example, and Graph D is a characteristic graph of oleic acid.
As can be seen from the graph C, the sample according to the present example shows that the hydrophilic group appearing at about 3500 cm -1 is relatively small. Thus, it can be confirmed that the phosphor according to the present example has excellent moisture resistance. This is a result of the hydrophobic coating layer formed on the surface of the K 2 SiF 6 : Mn 4+ fluorescence body.
FIG. 6 is a graph showing the PL characteristic of the phosphor prepared according to the preferred embodiment of the present invention.
Referring to FIG. 6, the excitation wavelength? Ex is set to 450 nm, and two samples are prepared for comparison. First, the pure K 2 SiF 6 : Mn 4+ fluorescence body before the solvent thermoacoustic method is performed is prepared as one sample, and the other sample is the sample prepared according to Production Example 1.
Two samples are immersed in water for moisture resistance measurement of two phosphor samples. The concentration of each sample is fixed at 6250 ppm. After soaking in water for 15 days, the change in emission intensity is measured. It can be confirmed that the sample prepared according to the preparation example of this example maintains the emission intensity at the red wavelength band. However, in the case of the fluorescent body in which the hydrophobic coating layer is not formed, the hydrolysis reaction with water and the elution of Mn It can be confirmed that the light emitting function is damaged. Accordingly, it can be confirmed that the phosphor prepared according to this embodiment has excellent moisture resistance.
Production Example 2
The phosphor was produced in the same manner as in Production Example 1 above. However, the reaction is induced by keeping in an oven maintained at 140 ° C for 1 hour in the solvent thermo-synthetic process.
7 is a PL graph showing the characteristics of the phosphor formed by Production Example 2 of the present invention.
Referring to Fig. 7, Graph A shows the characteristics of the phosphor formed by Production Example 1 of this embodiment, and Graph B shows the characteristics of the phosphor formed by Production Example 2. Fig. Also, Graph C shows the characteristics of a pure K 2 SiF 6 : Mn 4+ phosphor in which a hydrophobic coating layer is not formed.
As shown in FIG. 7, the graph A shows the highest light emission intensity, and the graph C shows the lowest light emission intensity. This indicates that the crystallinity of the K 2 SiF 6 : Mn 4+ phosphor is improved by the heat applied in the heat treatment of the solvent.
Production Example 3
The same solvent thermal synthesis method as in Production Example 1 is used. 0.7 g of the phosphor of Production Example 1 is mixed in 25 ml of ethanol, 9 ml of oleic acid is mixed together, and a sample is prepared by a solvent thermal synthesis method. That is, in Production Example 1, 3 ml of oleic acid was added, but in this production example, the amount of oleic acid was increased to 9 ml.
Production Example 4
The same solvent thermal synthesis method as in Production Example 1 is used. 0.7 g of the phosphor of Production Example 1 is mixed in 25 ml of ethanol, 5 ml of oleic acid are mixed together, and a sample is prepared by a solvent thermal synthesis method
Production Example 5
The same solvent thermal synthesis method as in Production Example 1 is used. 0.7 g of the phosphor of Production Example 1 is mixed into 25 ml of ethanol, and then 3 ml of oleic acid is added. The difference from Production Example 1 was that the reaction was sufficiently induced by maintaining in an oven maintained at 160 캜 for 6 hours.
FIG. 8 is a graph showing the characteristics of phosphors manufactured according to a preferred embodiment of the present invention.
8, the graph A shows the characteristics of a pure K 2 SiF 6 : Mn 4+ phosphor in which the hydrophobic coating layer is not formed, and the graph B shows the characteristics of the K 2 SiF 6 : Mn 4+ phosphor prepared in Production Example 1 FIG. Graph C shows the characteristics of the K 2 SiF 6 : Mn 4+ phosphor produced by Production Example 4, and Graph D shows the characteristics of the K 2 SiF 6 : Mn 4+ phosphor formed by Production Example 6 .
In FIG. 8, when the temperature of the synthesis is increased or the amount of oleic acid is slightly increased in the solvent thermal synthesis method, the increase in the light emission intensity is insignificant. However, when the hydrophobic coating layer is formed by the solvent thermo-synthetic method, the luminescence intensity increases under any condition.
Production Example 6
A white light emitting device is manufactured using a K 2 SiF 6 : Mn 4+ phosphor. First, K 2 SiF 6 : Mn 4+ in which a hydrophobic coating layer was not formed was prepared, and a K 2 SiF 6 : Mn 4+ phosphor in which a hydrophobic coating layer formed according to Preparation Example 1 of the present example was formed was prepared to prepare a white light- do. For the realization of white light, Sr 2 SiO 4 : Eu 2+ which is a silicate green phosphor is used.
In the manufacturing process, each phosphor is mixed and dispersed in a weight ratio of 1 to 10, and injected and filled into the upper portion of the light emitting diode chip. And then heated at 150 캜 for 1 hour to produce a white light emitting device having an excitation wavelength of 450 nm. The prepared white light emitting diodes were subjected to a humidity test within 450 hours at a temperature of 85 캜, a relative humidity of 85%, and a current of 120 mA.
Table 1 shows the moisture resistance characteristic results of each of the formed white light emitting devices.
Rate of change
(%)
Sample 1 in Table 1 is a white light emitting device using a pure K 2 SiF 6 : Mn 4+ phosphor and
As shown in Table 1, each sample shows a change in luminous intensity at a lapse of 150 hours. However, even when the moisture resistance test time elapses, the change in the luminous intensity of the
According to the present invention described above, a hydrophobic coating layer is formed on the surface of the fluoride fluorescent body. The moisture-absorbing property of the fluoride-based fluorescent material is remarkably improved by the formation of the hydrophobic coating layer. This is because the hydrophobic coating layer blocks the degradation of the properties of the fluorescent body due to moisture, thereby forming the fluoride-based fluorescent substance having improved moisture resistance. Further, the light-emitting element formed using the same can ensure excellent moisture resistance.
Claims (13)
And a hydrophobic coating layer formed on the surface of the fluoride fluorescent body.
[Chemical Formula 1]
A 2 BF 6 : Mn 4+
Wherein A is at least one element selected from the group consisting of Li, Na, K, Rb and Cs as a monovalent metal cation, B is a tetravalent cation and is selected from the group consisting of Ge, Si, Sn and Ti At least one element.
The above-
A fluoride fluorescent body represented by the following formula (2); And
And a hydrophobic coating layer formed on the surface of the fluoride fluorescent body.
(2)
A 2 BF 6 : Mn 4+
Wherein A is at least one element selected from the group consisting of Li, Na, K, Rb and Cs as a monovalent metal cation, B is a tetravalent cation and is selected from the group consisting of Ge, Si, Sn and Ti At least one element.
Introducing an organic substance having a hydrophobic group into an organic solvent into which the fluoride fluorescent body is incorporated; And
And bonding the organic material having the hydrophobic group to the fluoride fluorescent body to form a hydrophobic coating layer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200095207A (en) * | 2019-01-31 | 2020-08-10 | 한국화학연구원 | Fabrication Method of Metal Fluoride-based Phosphors |
| KR20210049260A (en) * | 2019-10-25 | 2021-05-06 | 한국화학연구원 | Selective Fabrication Method of Metal Fluoride-based Phosphors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102409189B1 (en) * | 2017-03-17 | 2022-06-15 | 쑤저우 레킨 세미컨덕터 컴퍼니 리미티드 | Phosphor, light emitting device package and lighting apparatus comprising the same |
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| WO2007102394A1 (en) * | 2006-03-09 | 2007-09-13 | Konica Minolta Medical & Graphic, Inc. | Nano-phosphor and nano-phosphor composite |
| KR20120097697A (en) * | 2011-02-25 | 2012-09-05 | 삼성전자주식회사 | Light emitting diode |
| KR20140017727A (en) * | 2012-07-31 | 2014-02-12 | 엘지디스플레이 주식회사 | Fluorescent nanocomposite and preparation method thereof |
| JP2014141684A (en) * | 2012-12-28 | 2014-08-07 | Shin Etsu Chem Co Ltd | Surface treatment method of fluophor |
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| WO2007102394A1 (en) * | 2006-03-09 | 2007-09-13 | Konica Minolta Medical & Graphic, Inc. | Nano-phosphor and nano-phosphor composite |
| KR20120097697A (en) * | 2011-02-25 | 2012-09-05 | 삼성전자주식회사 | Light emitting diode |
| KR20140017727A (en) * | 2012-07-31 | 2014-02-12 | 엘지디스플레이 주식회사 | Fluorescent nanocomposite and preparation method thereof |
| JP2014141684A (en) * | 2012-12-28 | 2014-08-07 | Shin Etsu Chem Co Ltd | Surface treatment method of fluophor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200095207A (en) * | 2019-01-31 | 2020-08-10 | 한국화학연구원 | Fabrication Method of Metal Fluoride-based Phosphors |
| KR20210049260A (en) * | 2019-10-25 | 2021-05-06 | 한국화학연구원 | Selective Fabrication Method of Metal Fluoride-based Phosphors |
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