KR101510124B1 - BLUISH GREEN EMITTING PHOSPHORS FOR HIGH COLOR RENDERING AND HIGH EFFICIENT WHITE LEDs AND LEDs USING THE SAME - Google Patents

Abstract

The present invention relates to a bluish green light-emitting fluorescent body for a white light-emitting diode device and to a white LED device using the same. The bluish green light-emitting fluorescent body of the present invention has high efficiency and excellent temperature stability according to an optimal combination of cation and anion components and the composition ratio thereof. A lattice defection in a crystal structure is minimized so that similar or excellent light-emitting properties are ensured compared to a commercial fluorescent body product. In addition, when a green fluorescent body and a red fluorescent body are mixed and coated on a bluish green LED, a whit LED device is produced by further containing the bluish green light-emitting fluorescent body, thereby having excellent color rendition. Bluish green is massively used instead of red which is disadvantageous to light efficiency, thereby remarkably improving intensity of light.

Description

TECHNICAL FIELD [0001] The present invention relates to a blue light-emitting phosphor for a white light-emitting diode, and a white LED using the blue light-

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blue light-emitting phosphor for a white light emitting diode device and a white light emitting diode (LUMINESCENCE CONVERSION LIGHT EMITTING DIODE) device using the same. More particularly, The present invention relates to a blue-green light-emitting phosphor that has a specific crystal structure at a thermodynamic synthesis temperature and minimizes lattice defects in the crystal by optimizing a composition ratio thereof. The blue-green light- And a white LED device having excellent color rendering properties and remarkably improved luminescence brightness compared to conventional methods.

The phosphor plays a role in converting the energy of the excitation source into the energy of the visible light and is essential for image display of various display devices. The efficiency and the color reproduction range of the phosphor are directly related to the efficiency and color reproduction range of display products and lighting products It is the main factor.

As one of the diode elements emitting white light, there is a blue LED element. This is a method in which blue light emitted from the device is mixed with yellow light emitted from the phosphor by applying a phosphor emitting yellow light with the blue light as an excitation source to the device emitting blue light. That is, an LED element emitting white light is a method of applying a blue light emitted from a device and a secondary light source emitted from the phosphor by applying a phosphor to the LED, and a method of obtaining a white light by applying a YAG: Ce phosphor emitting yellow to a blue LED [ U.S. Patent No. 6,069,440].

However, this method has a disadvantage in that it is accompanied by quantum defects generated while using secondary light and efficiency reduction due to the re-emission efficiency, and color rendering is not easy. Accordingly, a conventional white LED backlight is a combination of a blue LED chip and a yellow phosphor, and is limited in the extent that it can be used for a screen of a mobile phone or a notebook PC because green and red components are lacking and therefore unnatural colors are expressed. Nevertheless, it has been widely commercialized because of its advantages of being easy to drive and being remarkably inexpensive.

On the other hand, for white LEDs, the development of phosphors that emit visible light by excitation by an excitation source having high energy such as ultraviolet light or blue light has become mainstream. However, the conventional phosphor has a problem that the brightness of the phosphor is lowered when the phosphor is exposed to an excitation source. In recent years, as a phosphor whose hostility is low, the phosphor having a host crystal of silicon nitride- A nitride or a phosphor has attracted attention as a material capable of shifting excitation light or light emission toward the long wavelength side.

Particularly, in 2004, a green phosphor of β-sialon (Eu) was developed in 2005 following CaAlSiN ₃ : Eu red phosphor which is a pure nitride. When such a phosphor is combined with a blue LED chip, the color purity is improved. Particularly, since the phosphor has excellent durability and small temperature change, it can contribute to long life and reliability improvement of the LED light source.

Recently, a new LED for illumination has been developed by combining a blue LED chip, a Lu ₃ Al ₅ O ₁₂ : Ce green phosphor and a red phosphor CaAlSiN ₃ : Eu (Caesen) Yellow phosphor 520 to 570 nm, and red phosphor 650 nm to generate three primary color components. However, these combinations are not easy to maintain color rendering at 90 or more, and in order to appropriately select the white coordinates, the red phosphors enter relatively much, and thus the emission intensity is lowered.

On the other hand, in the case of oxynitride phosphors, much research has been carried out since 2009, but the commercialization has been delayed due to the lack of reliability due to the occurrence of lattice defects due to the combination of unsafe oxygen ions and nitrogen ions.

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The present inventors have made efforts to solve the problems of the prior art. As a result, the inventors have found that optimizing the components of cations and anions and their composition ratios can be used not only in a crystal structure of a homogeneous phase at a thermodynamic synthesis temperature but also in a multi- In the production of a white LED obtained by mixing a green phosphor and a red phosphor on a conventional blue LED by applying a stable blue green light emitting phosphor with a high efficiency by minimizing defects and mixing the blue green light emitting phosphor of the present invention, The device was fabricated, and the color rendering index and luminous flux improvement of the manufactured white LED device were confirmed, thereby completing the present invention.

An object of the present invention is to provide a blue-green light-emitting phosphor having high efficiency, excellent temperature stability, and minimized lattice defects.

Another object of the present invention is to provide a white LED device which is produced by mixing a green phosphor and a red phosphor on a blue LED, further comprising the blue-green light emitting phosphor, and has excellent color rendering properties and high emission luminance.

Still another object of the present invention is to provide a use of a white LED device.

The present invention provides a blue-green light-emitting phosphor having a composition formula of the following formula (1).

Formula 1

A _a B _b O _c N _d C _e : RE _h

B is at least one or more elements selected from the group consisting of Si, Ge, and Sn; C is at least one element selected from the group consisting of C, Cl, F And Br, and RE is at least one or more elements selected from the group consisting of Eu, Ce, Sm, Er, Yb, Dy, Gd, Tm, Lu, Pr, Nd, Pm and Ho, 0 <b? 15, 0? C? 15, 0? D? 20, 0? E? 10, 0? H? 10.

The present invention provides a blue-green light-emitting phosphor having a composition formula of the following formula (2).

(2)

A _a B _b O _c N _d C _e D _f e _g : RE _h

B is at least one or more elements of Si, Ge, and Sn; C is at least one element selected from the group consisting of C, Cl, F, Br E is at least one or more elements selected from the group consisting of P, As, Bi, Sc, Y and Lu, and RE is at least one element selected from the group consisting of Li, And 0 < c < 15, 0 < b < 15, and 0 < c < 15, 0 <d? 20, 0? E? 10, 0 <f? 10, 0 <g? 10, 0?

The blue-green light-emitting phosphor of the present invention has a stable crystal structure at the thermodynamic synthesis temperature by optimizing the components of the cation and the anion and the composition ratio thereof, optimizing the ion ratio between O and N elements in particular, Thereby minimizing defects.

Thus, the blue-green light emitting phosphor of the present invention is characterized in that when the C element is any one of C, F, Cl, and Br in the composition formula of Formula 1 and the molar ratio thereof is 0.01? E? 10, Ba _2.9 Si ₆ O _{3 N 8 C 0.01: Eu 0.1} , Ba 2 .9 Si 5 .9 O 3 N 8 C 0 .1: Eu 0 .1, Ba 2 .9 Si 6 O 3 N 8 C 1: Eu 0 .1, Ba _{2 .9} Si ₆ O ₃ N ₈ C ₅ : Eu _{0 .1} , Ba _{2 .9} Si ₆ O ₃ N ₈ C ₁₀ : Eu _{0 .1} , Ba _{2 .9} Si ₆ O ₃ N ₈ F _{0 .01} : Eu _{0 .1} , Ba _{2 .95} Si ₆ O ₃ N ₈ F _{0 .1} : Eu _{0 .1,} Ba _{2 .9} Si ₆ O ₃ N ₈ F ₁ : Eu _{0 .1} , Ba _2.9 Si ₆ O ₃ N _{8 F 5: Eu 0.1, Ba} 2 .9 Si 6 O 3 N 8 F 10: Eu 0 .1, Ba 2 .9 Si 6 O 3 N 8 Cl 0 .01: Eu 0 .1, Ba 2.95 Si 6 O _{3 N 8 Cl 0.1: Eu 0.1} , Ba 2 .9 Si 6 O 3 N 8 Cl 1: Eu 0 .1, Ba 2 .9 Si 6 O 3 N 8 Cl 5: Eu 0 .1, Ba 2 .9 Si _{6 O 3 N 8 Cl 10:} Eu 0 .1, Ba 2.9 Si 6 O 3 N 8 Br 0.01: Eu 0.1, Ba 2 .95 Si 6 O 3 N 8 Br 0 .1: Eu 0 .1, Ba 2. ₉ Si ₆ O ₃ N ₈ Br ₁ : Eu _{0 .1} , Ba _2.9 Si ₆ O ₃ N ₈ Br ₅ : Eu _0.1 and Ba _{2 .9} Si ₆ O ₃ N ₈ Br ₁₀ : Eu _{0 .1} Which one is chosen I am preferable. At this time, in the blue green light emitting phosphor of the present invention, the element B in the composition formula of the formula (1) is preferably Si.

Further, in the blue-green light-emitting fluorescent material of the present invention, the element A is Ba in the composition formula of the formula 1, more preferably, the Ba ion site is filled with Mg ions to stabilize the crystallinity. Is incorporated at 0.01 &lt; = a &lt; = 1,
Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 : Eu _0.15 , Ba _2.34 Mg _0.11 Si _5.45 O _2.89 N ₇ F _0.22 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 : Eu _0.15 , Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 : Eu _0.15 and Ba _11.55 Mg _1.3 Si _2.1 O _5.3 N _1.4 F _0.67 : Eu _0.15 .

The blue-green light-emitting fluorescent material of the present invention is preferable when RE is Eu and 0.01? H? 10 in the composition formula of the formula (1).

Further, the blue-green light emitting phosphor of the present invention is mixed with Mg 0.01? A'? 1 in the A element Ba in the composition formula of the formula (2), the D element is K 0.01? F? 10 and the E element is P When it is incorporated in the range of 0.01? G? 10,
Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.1 P _0.03 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.15 P _0.05 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.1 P _0.3 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K ₃ P ₁ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K _0.1 P _0.03 : Eu _0.15 , Ba _1.84 Mg _0.11 Si ₅ O _2.695 N _8.33 F _0.22 K _0.15 P _0.05 : Eu _0.15, Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K _0.3 P _0.1 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K ₁ P ₃ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.2 K ₃ P ₁ : Eu _0.15 and Ba _2.79 Mg _0.11 Si ₆ O _3.62 N ₈ F _0.29 K _0.755 P _0.155 : Eu _0.1 .

As another preferred example of the blue-green light emitting phosphor of the present invention, in the composition formula of Formula 2, Mg 0.01? A? 1 is added to A element Ba and D element Li and K are added to C element F to satisfy 0.01? F? 10, and the E element is incorporated in the range of P 0.01? G? 10,
Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.32 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.72 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.145 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.7 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.5 P _0.1 Li _0.2 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.32 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.72 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _1.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.79 Mg _0.11 Si ₆ O _3.62 N ₈ F _0.66 K _0.465 P _0.155 Li _0.66 : Eu _0.15 , Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 and Ba _11.55 Mg _1.3 Si _2.1 O _5.3 N _1.4 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 .

Or more of the blue-green light-emitting fluorescent substance has an excitation source in a wavelength region of 300 to 500 nm, emits an emission wavelength of 460 to 540 nm, and has a light emission center wavelength of 490 to 510 nm.

As a result of the particle size distribution (PSA) measurement, the blue-green light emitting phosphor of the present invention has a particle size of 1 to 10 mu m when D10, 10 to 30 mu m when D50, and 20 to 70 mu m when D90 It meets the requirements for LED device applications.

Further, the present invention provides a white LED device manufactured by mixing a green phosphor and a red phosphor on a blue LED, and further comprising the blue light-emitting phosphor of the present invention.

At this time, the white LED device of the present invention may be a type in which a green phosphor, a red phosphor, and a blue-green light emitting phosphor are dispersedly coated on the blue LED; Conformal type; Or a remote type LED package.

In the above white LED device, the preferable content of the blue-green light-emitting fluorescent substance of the present invention is 0.1 to 99 parts by weight based on 100 parts by weight of the epoxy resin or encapsulant. At this time, the white LED device of the present invention maintains a CRI (Reflectance Index) of 65 to 98 at a color temperature (CCT) of 2700 to 6500 K, thereby improving the luminous flux.

Further, the white LED device of the present invention can be applied to various fields such as electronic parts field of display backlight or illumination selected from the group consisting of a head lamp for a vehicle, an indoor lamp, an outdoor lamp, a street light, a billboard light, a stadium light, And is useful as a light source for applications.

The present invention can provide a phosphor emitting blueish-green with high efficiency and excellent in temperature stability by the optimum combination of components of cation and anion and composition ratio thereof in the phosphor.

Thus, the blue-green light-emitting fluorescent substance of the present invention can be used as a substitute for a conventional commercial fluorescent substance because it has excellent temperature characteristics as well as equivalent or excellent light emission characteristics as compared with commercial fluorescent substance products.

Further, when the blue LED is manufactured by mixing a green phosphor and a red phosphor on a blue LED, the green phosphor and the red phosphor may further contain the blue light-emitting phosphor of the present invention to produce a white LED device, And a large amount of blue-green is used instead of red, which is disadvantageous to the light efficiency, it is possible to provide a white LED having a remarkably high luminous intensity.

Therefore, the white LED device of the present invention is useful as a light source used in an illumination field selected from the group consisting of electronic parts of a display backlight, a head lamp for a vehicle, an interior light, a medical light source, a display light source, and an agricultural light source.

1 is an excitation spectrum and an emission spectrum of a blue-green light-emitting fluorescent substance obtained when the C element is C and 0.01? E? 10 in the composition formula of the formula 1 of the present invention,
2 is an excitation spectrum and an emission spectrum of a blue-green light-emitting fluorescent substance obtained when the element C is F and 0.01? E? 10 in the composition formula of the present invention,
3 is an excitation spectrum and an emission spectrum of a blue-green light-emitting fluorescent substance obtained when the C element is Cl and 0.01? E? 10 in the composition formula of the present invention,
4 is an excitation spectrum and an emission spectrum of a blue-green light-emitting fluorescent substance obtained when the element C is Br and 0.01? E? 10 in the composition formula of the formula 1 of the present invention,
FIG. 5 is an excitation spectrum and an emission spectrum of the blue-green light-emitting fluorescent substance obtained when the element A is incorporated in Ba into Mg 0.01? A'? 1 in the composition formula of the formula 1 of the present invention,
FIG. 6 is a graph showing the relationship between the C element F and the D element, K 0.01 ≤ f ≤ 10 and the E element P 0.01 ≤ g ≤ 1, 10, the excitation spectrum and the luminescence spectrum of the blue-green light-emitting fluorescent substance obtained are shown,
Fig. 7 is a graph showing the relationship between the C element F and the D element Li and K, 0.01 ≦ f ≦ 10, and the E element P 0.01 &Lt; = g &lt; / = 10, and the excitation spectrum and emission spectrum of the obtained blue-green light-
FIG. 8 is a graph showing the relationship between (a) 800 times and (b) 3000 magnifications of Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 phosphor as _blue- SEM picture,
FIG. 9 shows the results of the particle size distribution (PSA) measurement of the blue light-emitting phosphor of the present invention,
Fig. 10 is a graph of component distribution showing the results of fluorescence X-ray analysis of the blue-green light-emitting fluorescent substance of the present invention,
11 is a _graph showing changes in luminescence intensity depending on the temperature of Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue green light emitting phosphor of the present invention,
Figure 12 (a) of the present invention, _{Ba 2.84 Mg 0.11 Si 5.95 O 3.4} N 8.33 F 0.22: Eu 0.15, (b) Ba 2.84 Mg 0.11 Si 5.9 O 3.64 N 7.93 F 0.67 K 0.48 P 0.16 Li 0.67: Eu 0.15, (c) Mg _2.95 Si _5.95 O _3.4 N _8.33 F _0.22 : Eu _0.15 XRD data of blue-green light-emitting phosphor,
13 is a basic model of the crystal structure according to the XRD result of the blue-green light-emitting phosphor of Fig. 12 (a)
14 is _{Ba 2.84 Mg 0.11 Si 5.9 O 3.64} N 7.93 F 0.67 K 0.48 P 0.16 Li 0.67 of the present invention: color rendering index of light spectrum in the Eu _0.15 cyan manufactured using a light-emitting phosphor white LED with a commercial white LED index ( CRI) 90 under the 5000K standard,
Fig. 15 The white LED device fabricated by using the blue light emitting phosphor of Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 of the present invention exhibited the light observed under a 5000K color rendering index (CRI) Spectrum,
16 is a schematic configuration diagram of the white LED device of the present invention,
17 is a schematic diagram of a white LED device in which phosphors are manufactured in a dispersive type as a first embodiment of manufacturing the device of the present invention,
FIG. 18 is a schematic diagram of a white LED device in which phosphors are fabricated in a conformal type as a second embodiment of manufacturing the device of the present invention,
Fig. 19 is a schematic configuration diagram of a white LED element in which a phosphor is manufactured as a remote type as a third embodiment of the device fabrication of the present invention. Fig.

Hereinafter, the present invention will be described in detail.

The present invention provides a blue-green light-emitting phosphor having a composition formula of the following formula (1).

Formula 1

A _a B _b O _c N _d C _e : RE _h

Wherein A is at least one or more elements selected from the group consisting of Be, Mg, Ca, Sr, Ba and Ra, B is at least one element selected from the group consisting of Si, Ge and Sn, C is C or Cl, F And Br, and RE is at least one or more elements selected from the group consisting of Eu, Ce, Sm, Er, Yb, Dy, Gd, Tm, Lu, Pr, Nd, Pm and Ho, 0 <b? 15, 0? C? 15, 0? D? 20, 0? E? 10, 0? H? 10.

Also, the present invention provides a blue-green light-emitting phosphor having a composition formula of the following formula (2).

(2)

A _a B _b O _c N _d C _e D _f e _g : RE _h

B is at least one or more elements of Si, Ge, and Sn; C is at least one element selected from the group consisting of C, Cl, F, Br E is at least one or more elements selected from the group consisting of P, As, Bi, Sc, Y and Lu, and RE is at least one element selected from the group consisting of Li, And 0 < c < 15, 0 < b < 15, and 0 < c < 15, 0 <d? 20, 0? E? 10, 0 <f? 10, 0 <g? 10, 0?

Or more of the blue-green light-emitting fluorescent substance has a wavelength range of 300 to 500 nm as an excitation source, emits an emission wavelength of 460 to 540 nm, and the emission center wavelength satisfies a range of 490 to 510 nm. Can be applied to a white LED device.

In other words, the blue-green light-emitting fluorescent substance of the present invention is a blue light-emitting fluorescent substance which can stabilize crystal lattice defects generated in combination of N ions and O ions, which are anions, in accordance with composition ratios of Ba and Mg, And the component of the anion and the composition ratio thereof are optimized.

Thus, the phosphors of FIGS. 1 to 4 can be confirmed to produce blue-green (cyan or blue-green) phosphors through excitation spectra and emission spectral results according to the preferable combinations of the respective components and their composition ratios in the composition formula of the formula (1).

Specifically, the blue-green light-emitting fluorescent substance of the present invention is preferably a fluorescent substance according to the composition formula of the following formula 1-2.

1-2

A _a B _b O _c N _d C _e : RE _h

Wherein A is Ba, B is Si, C is any one of C, Cl, F and Br elements and RE is Eu, wherein 0.05? A? 15, 0.5? B? 15, 0.1? c? 15, 0.67? d? 20, 0.01? e? 10, and 0.01? h? 10.

The blue-green light-emitting fluorescent material according to the formula 1-2 composition has a wavelength range of 300 to 500 nm as an excitation source, emits an emission wavelength of 460 to 540 nm, and has a emission center wavelength of 490 to 500 nm. It has a half width and can realize excellent color.

Thus, as an example of the blue-green light emitting phosphor according to the above formula 1-2 the composition formula, the element C and has any one of the elements of C, F, Cl, Br, when the 0.01 ≤e≤ 10 il The molar ratio, Ba _2.9 Si _{6 O 3 N 8 C 0.01:} Eu 0.1, Ba 2 .9 Si 5 .9 O 3 N 8 C 0 .1: Eu 0 .1, Ba 2 .9 Si 6 O 3 N 8 C 1: Eu 0 .1 Ba _{2 .9} Si ₆ O ₃ N ₈ C ₅ : Eu _{0 .1} , Ba _2.9 Si ₆ O ₃ N ₈ C ₁₀ : Eu _0.1 , Ba _{2 .9} Si ₆ O ₃ N ₈ F _{0 .01} : Eu _{0 1} , Ba _{2 .95} Si ₆ O ₃ N ₈ F _{0 .1} : Eu _{0 .1,} Ba _{2 .9} Si ₆ O ₃ N ₈ F ₁ : Eu _{0 .1} , Ba _2.9 Si ₆ O ₃ N ₈ F _{5: Eu 0.1, Ba 2 .9} Si 6 O 3 N 8 F 10: Eu 0 .1, Ba 2 .9 Si 6 O 3 N 8 Cl 0 .01: Eu 0 .1, Ba 2.95 Si 6 O 3 N _{8 Cl 0.1: Eu 0.1, Ba} 2 .9 Si 6 O 3 N 8 Cl 1: Eu 0 .1, Ba 2 .9 Si 6 O 3 N 8 Cl 5: Eu 0 .1, Ba 2 .9 Si 6 O _{3 N 8 Cl 10: Eu 0} .1, Ba 2.9 Si 6 O 3 N 8 Br 0.01: Eu 0.1, Ba 2 .95 Si 6 O 3 N 8 Br 0 .1: Eu 0 .1, Ba 2 .9 Si ₆ O ₃ N ₈ Br ₁ : Eu _{0 .1} , Ba _2.9 Si ₆ O ₃ N ₈ Br ₅ : Eu _0.1 and Ba _{2 .9} Si ₆ O ₃ N ₈ Br ₁₀ : Eu _{0 .1} which Thou.

Another preferred phosphor of the blue-green light-emitting phosphor of the present invention is a phosphor according to the composition formula of the following formula 1-3.

1-3

A _a B _b O _c N _d C _e : RE _h

Wherein A is Ba and Mg, B is Si, C is any one of C, Cl, F and Br and RE is Eu, wherein 0.05? A? 15, 0.5? B? 15, 0.1 ? C? 15, 0.67? D? 20, 0.01? E? 10, and 0.01? H? 10.

Blue-green light emitting phosphor according to the formula of Formula 1-3 are cations Ba ^{2 +} ions in place, the Ba ^{2 +} ions than the ion radius is small Mg ^{2 +} ions (atomic radius of 160 pm) is further incorporated into the matrix (lattice) , It is possible to minimize the lattice defects in the crystal structure of the single phase to achieve high efficiency and increase in temperature stability.

At this time, the mixing amount of Mg ions is preferably from 0.01 to 1 mol, and when the molar ratio is less than 0.01 or exceeds 1, the optical characteristics are deteriorated.

5 shows the excitation spectrum and luminescence spectrum of the obtained blue-green light-emitting fluorescent substance when the element A is incorporated into Ba in Mg 0.01? A'? 1 in the composition formula of the formula 1 of the present invention. The wavelength range of 300 to 500 nm is excited by excitation Circle, emitting an emission wavelength of 460 to 540 nm, and satisfying a range of the emission center wavelength of 490 to 510 nm.

In the embodiment of the present invention, as the phosphor according to the composition formula 1-3, Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 : Eu _0.15 , Ba _2.34 Mg _0.11 Si _5.45 O _2.89 N ₇ F _0.22 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 : Eu _0.15 , Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 : Eu _0.15 and Ba _11.55 Mg _1.3 Si _2.1 O _5.3 N _1.4 F _0.67 : Eu _0.15 .

The blue-green light-emitting phosphor having the composition formula of Formula 2 of the present invention is mixed with Mg 0.01? A'? 1 in the A element Ba in the composition formula of Formula 2, and the element D is mixed with K 0.01? F? 10, and the E element is incorporated in the range of P 0.01? G? 10,
Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.1 P _0.03 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.15 P _0.05 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.1 P _0.3 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K ₃ P ₁ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K _0.1 P _0.03 : Eu _0.15 , Ba _1.84 Mg _0.11 Si ₅ O _2.695 N _8.33 F _0.22 K _0.15 P _0.05 : Eu _0.15, Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K _0.3 P _0.1 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K ₁ P ₃ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.2 K ₃ P ₁ : Eu _0.15 and Ba _2.79 Mg _0.11 Si ₆ O _3.62 N ₈ F _0.29 K _0.755 P _0.155 : Eu _0.1 .

6 shows an excitation spectrum and an emission spectrum of the blue-green light-emitting fluorescent substance obtained by the above composition.

As another preferred example of the blue-green light-emitting phosphor of the present invention, Mg 0.01? A?? 1 is incorporated into A element Ba in the composition formula of Formula 2, and D element Li and K are added to C element F to 0.01? F &Lt; / = 10, and the E element is incorporated in the range of P 0.01 &lt; = g &lt; = 10,
Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.32 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.72 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.145 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.7 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.5 P _0.1 Li _0.2 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.32 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.72 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _1.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.79 Mg _0.11 Si ₆ O _3.62 N ₈ F _0.66 K _0.465 P _0.155 Li _0.66 : Eu _0.15 , Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 and Ba _11.55 Mg _1.3 Si _2.1 O _5.3 N _1.4 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 .

Fig. 7 shows the excitation spectrum and the luminescence spectrum of the blue-green light-emitting fluorescent substance obtained by the above composition.

The blue-green light-emitting fluorescent material according to the above formula (2) has an excitation source in a wavelength range of 300 to 500 nm, emits an emission wavelength of 460 to 540 nm, and has a center wavelength of 490 to 500 nm.

Figure 8 is a Ba-green (BG) emitting phosphor of the present invention _{5.32 Mg 0.53 Si 12.1 O 3.3 N} 18.2 F 0.67 K 0.48 P 0.16 Li 0.67: (a) for the Eu _0.15 phosphor 800 times, and (b) a 3000 magnification SEM As a photograph, the particle shape can be confirmed.

9 shows the results of the particle size distribution (PSA) measurement of the blue-green light-emitting fluorescent substance of the present invention. Dispersion (D10): 1 to 10 탆, D20: 5 to 15 탆, D30: 10 to 20 탆, D40 D50: 10 to 30 탆, D60: 15 to 30 탆, D70: 15 to 35 탆, D80: 20 to 40 탆, D90: 20 to 70 탆, D100: .

Particularly, since D50 satisfies the particle size of 10 to 30 mu m, it satisfies the particle size distribution required in the LED field, and if it is out of the above range, the particle size becomes too large, causing precipitation. Therefore, the blue-green light-emitting fluorescent material of the present invention is suitable for use as a phosphor for LED applications.

10 is a graph showing the results of fluorescent X-ray analysis of the blue-green light-emitting phosphor of the present invention, and it can be confirmed that a phosphor composed of elements of Ba, Mg, Si, O, N, F and Eu is produced.

11 is a _graph showing changes in luminescence intensity depending on the temperature of Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue green light emitting phosphor, It is possible to provide a phosphor excellent in efficiency and excellent in temperature stability and reliability by favorably controlling the emission center wavelength and crystal structure of the synthesized phosphor in accordance with the coupling ratio of Mg ²⁺ ions having a relatively small radius.

Figure 12 (a) of the present invention, _{Ba 2.84 Mg 0.11 Si 5.95 O 3.4} N 8.33 F 0.22: Eu 0.15, (b) Ba 2.84 Mg 0.11 Si 5.9 O 3.64 N 7.93 F 0.67 K 0.48 P 0.16 Li 0.67: Eu 0.15, (c) Mg _2.95 Si _5.95 O _3.4 N _8.33 F _0.22 : Eu _0.15 XRD data of the blue-green light-emitting phosphor, and FIG. 13 is a basic model of the crystal structure according to the XRD result of the blue-green light emitting phosphor of FIG. More specifically, Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 or Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 Eu The basic crystal structure of _0.15 blue green light emitting phosphor is a modification of an orthorhombic structure, and it is a structure that can take various shapes by the combination of atoms set to increase the degree of covalency, and can easily form lattice defects. Therefore, in the present invention, Mg ions are partially substituted for Ba ions and, in the case of anions, halogen ions are additionally used to minimize lattice defects that can occur in the process. Therefore, as shown in FIG. 12, it can be seen that the crystallinity is improved. At this time, the reflectance of the x-ray at (1,1,1) plane as compared with the (3,1,1) Can be increased by 30% or more.

On the other hand, the crystal structure of the Mg _2.95 Si _5.95 O _3.4 N _8.33 F _0.22 : Eu _0.15 phosphor in (c) of FIG. 12 (c) shows a remarkable change such as the formation of a new phase as a phosphor containing Mg ions of 20% . Thus, the blue light emission intensity of the present invention achieves the maximum light emission intensity when Ba ions contain less than 10% of Mg ions.

It is possible to provide a high-reliability blue-green phosphor having a quantum efficiency of 90% or more through adjustment of anion mixing ratio and an improvement of a process.

The present invention relates to: 1) a bivalent metal ion of an alkaline earth metal; Si ions; And a metal salt containing Eu ions are quantitatively determined and then mixed to prepare a raw material salt for preparing a phosphor; And

2) heat-treating the mixed raw salt in a reducing atmosphere controlled at 1000 to 1600 ° C and a reducing gas of 100 to 1000 sccm, and a process for producing any one of the blue green light emitting phosphors selected from the general formula .

Among the production methods of the present invention, as the raw material salt for forming the blue-green light-emitting fluorescent substance matrix in the step 1), the metal element M has a phosphor structure and properties according to a combination of a divalent metal ion of an alkaline earth metal and an ionic radius different in composition Optimize.

Thus, as a divalent alkaline earth metal ions, preferably Ba ^{2 +} ions alone or the Ba ^{2 +} in accordance with the ionic bond ratio of an ionic radius is relatively small Mg ^{2 +} ions, the light emission of the phosphor to be synthesized central wavelength and By making the crystal structure advantageous, it is possible to provide a phosphor excellent in efficiency and excellent in temperature stability and reliability.

The compound capable of forming the oxide of the metal element M is not particularly limited. However, the compound capable of forming the oxide of the metal element M is not particularly limited, but a carbonate, a nitrate, a sulfate, a nitrate, At least one alkaline earth metal compound selected from oxides, peroxides and hydroxides is preferable. More preferred are carbonates, oxides, hydroxides, and fluorides of alkaline earth metals. Particularly preferably, the alkaline earth metal compound is in the form of carbonate (MCO ₃ ). The properties of the alkaline earth metal compound are also not particularly limited, but a powder phase is preferable to a lump phase in order to produce a high-performance phosphor.

When the A element of the alkaline earth metal in the composition formula of the present invention is used in a concentration of 0.05 to 15 mol, a blue-green light-emitting phosphor can be obtained, and the molar concentration of element A is the same as or different from the molar concentration of oxygen element .

At least one or more of C, Si, Ge, and Sn elements may be used as a raw material salt for forming the blue-green light-emitting fluorescent substance matrix of the present invention. In a preferred embodiment of the present invention, 0.5 to 15 moles Concentration. The silicon compound used in the conventional phosphor composition is not particularly limited, but silicon nitride (Si ₃ N ₄ ), silicon diimide (Si (NH) ₂ ) or the like is preferable as a requirement for producing a high- Silicon oxide (SiO ₂ ) is used.

At this time, according to the molar ratio of the silicon compound corresponding to the element B in the composition formula of the formula 1 of the present invention, the phosphor is produced in association with the concentration of the nitrogen element.

At least one or more of the elements of Eu, Ce, Sm, Er, Yb, Dy, Gd, Tm and Lu may be used as the activator of the fluorescent substance provided by the present invention. In the example, the molar concentration of europium (Eu ^&lt; ^{2 +} & gt ^; ) ions is 0.01 to 10 molar as compared with the divalent metal containing an alkaline earth metal.

Further, in the production method of the present invention, a raw material salt of the above step 1), _{NH 4 Cl, KCl, MgCl 2} , SrCl 2, BaCl 2, BaF 2, SrF 2, CaF 2, NH 4 F, H 3 BO 3 , K ₃ PO _4, and KNO ₃ . The flux is preferably contained in an amount of 1% by weight or more and less than 10% by weight with respect to the total mass of the raw material salt. If the flux is less than 1% by weight, mixing of each compound is insufficient and the reaction may end unstably. If the amount of the flux is more than 10% by weight, impurities may act on the phosphor and it becomes difficult to wash the phosphor after the reaction.

Hereinafter, in the manufacturing method of the present invention, the mixed raw salt is heat-treated at a firing temperature of 1000 to 1600 占 폚 and a reducing gas atmosphere controlled at 100 to 1000 sccm, thereby producing a blue-green light emitting phosphor.

If the firing temperature is lower than 1000 ° C., the coloring efficiency is lowered. If the firing temperature is higher than 1600 ° C., the color purity is lowered and high-quality phosphors can not be obtained.

The reducing gas atmosphere is performed under a reducing gas atmosphere and a normal pressure condition, which are composed of a mixed gas of nitrogen and hydrogen. At this time, it is preferable that the mixture gas contains nitrogen and hydrogen at a mixing ratio of 95: 5 to 90:10. In particular, the firing time may vary depending on the firing temperature and the feed rate of the mixed gas. Can be controlled.

Further, the present invention provides a white LED device manufactured by mixing a green phosphor and a red phosphor on a blue LED, and further comprising the blue light-emitting phosphor of the present invention.

Fig. 14 is a _graph showing the relationship between the light spectrum of the white LED device and the commercial white LED device fabricated using the Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue green light emitting phosphor of the present invention, (CRI) 90 at a color temperature of 5000K.

Specifically, the red graph in FIG. 14 is the spectrum of the current commercial white LED device in which the CRI 90 is realized under the 5000K color temperature condition, and the blue graph is the spectrum of Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _{0.15 In} the case of the white LED device of the present invention, the spectrum of the red region is reduced and the overall luminous flux is improved.

Fig. 15 The white LED device fabricated using the Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue _0.67 : Eu _0.15 blue green light emitting phosphor of the present invention was observed under a color rendering index (CRI) As a light spectrum, it is confirmed that a light emitting region is formed in the vicinity of the 500 nm region, thereby improving the color rendering index (CRI) and realizing the white light of the device.

Thus, Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 or Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 The white LED device manufactured by further containing a blue light-emitting fluorescent substance in a green phosphor and a red phosphor has a color rendering index equivalent to that of a commercial white LED device CRI) but the luminous flux is improved to about 10%.

Therefore, the white LED device of the present invention can dramatically improve the color rendering property and the luminous flux while suppressing excessive use of the red phosphor component, thereby increasing the emission intensity of the LED.

More specifically, FIG. 16 is a schematic diagram of the white LED device of the present invention, in which a light emitting diode chip 104 for emitting photons in the blue wavelength region is raised on the LED lead frame 102, And the red phosphor are dispersed by mixing with the epoxy resin, and the blue light-emitting phosphor of the present invention is further contained, so that the light efficiency of the device can be increased.

The light emitting diode chip 104 emitting the photons in the blue wavelength region may be a UV chip of 300 to 420 nm or a blue chip of 420 to 480 nm as an excitation light source. In an exemplary embodiment of the present invention, A GaN LED element emitting blue light in a wavelength region is used.

The curing portion is formed by uniformly dispersing not only a green phosphor and a red phosphor but also a phosphor synthesized in the present invention in an epoxy resin or an encapsulant such as epoxy or silicone and then applying the resulting cured portion to the light emitting diode chip 104 And then cured at 100 to 160 ° C for 1 hour to be fixed.

At this time, the added amount of the blue-green light-emitting fluorescent substance of the present invention can be adjusted according to a desired color coordinate, but it is contained in an amount of 0.1 to 99 parts by weight based on 100 parts by weight of silicone, epoxy resin or encapsulant.

In addition, a green phosphor may be mixed in the hardened portion for white coloring, and the green phosphor may be contained in an amount of 3 to 50 parts by weight based on 100 parts by weight of the epoxy resin.

The white LED device of the present invention using the above-described blue-green light-emitting fluorescent substance maintains a color rendering index (CRI) of 65 to 98 at a color temperature (CCT) of 2700 to 6500K, which contributes to the improvement of luminous flux.

More particularly, the present invention relates to a light emitting device comprising: a dispersive type in which a green phosphor, a red phosphor and a blue green light emitting phosphor are dispersed and distributed on a blue LED; Conformal type; Or a remote type LED package.

At this time, FIG. 17 is a schematic diagram of a white LED device fabricated in a dispersive type in which phosphors are dispersed and distributed as a first embodiment of manufacturing the device of the present invention, and is manufactured using a conventional method.

Fig. 18 is a schematic view of a white LED device in which phosphors are fabricated in a conformal type as a second embodiment of manufacturing the device of the present invention, and is formed by agglomerating in the periphery of the chip.

Fig. 19 is a diagram showing a white LED device in which a phosphor is manufactured as a remote type according to a third embodiment of the device manufacturing method of the present invention. The remote type is a plate made of ceramic, polymer, PIG (Phosphor In Glass) .

The white LED device of the present invention can be applied to a lighting field selected from the group consisting of electronic parts of a display backlight or a head lamp, an interior lamp, an outdoor lamp, a streetlight, a billboard light, a stadium light, a medical light source, As shown in Fig.

Hereinafter, the present invention will be described in more detail with reference to Examples.

The present invention is intended to more specifically illustrate the present invention, and the scope of the present invention is not limited to these embodiments.

Example 1 Preparation of Blue-Green Phosphor and Property Evaluation

Each raw material salt was quantified and put into a ball mill, followed by ball milling with isopropyl alcohol as a solvent for 8 to 24 hours, followed by drying. Thereafter, hydrogen gas was fired at a temperature of 1300 占 폚 for 3 hours in a reducing atmosphere controlled at a flow rate of 100 sccm to prepare a phosphor. At this time, a flux was used.

The phosphors are prepared according to the molar ratio of the respective element ions in the composition formula of the formula (1), and the physical properties of the phosphors are shown in Tables 1 to 4 below.

From the properties of the phosphors of Tables 1 to 4 and the characteristics of excitation spectra and luminescence spectra of the phosphors obtained from the composition formula of Formula 1 in FIG. 1 to FIG. 5, the phosphors prepared according to the composition of the positive and negative ions, It was confirmed that a blue light emitting phosphor having an emission wavelength of 460 to 540 nm and an emission center wavelength of 490 to 500 nm was used as the excitation source in the 500 nm wavelength region.

Example 2 Preparation of Blue-Green Phosphor and Property Evaluation

The BaCO ₃ , MgF ₂ , Si ₃ N ₄ And Eu ₂ O ₃ were used in place of Eu ₂ O ₃ . The physical properties of the phosphor prepared above are shown in Table 5 below.

As can be seen in Table 5, a blue-green light-emitting phosphor having a luminescent center wavelength of 492 to 495 nm was prepared, and from the results of the evaluation of the physical properties thereof, the Ba ion sites were filled with Mg ions and the crystallinity was stabilized .

Example 3 Preparation of Blue-Green Phosphor and Property Evaluation

The phosphors were prepared in the same manner as in Example 1 except that the phosphors were composed of a composition according to the composition formula 2 shown in Table 6 below. The physical properties of the phosphor prepared above are shown in Table 6 and FIG.

Example 4 Preparation of Blue-Green Phosphor and Property Evaluation

The phosphors were prepared in the same manner as in Example 1 except that the phosphors were composed of a composition according to the composition formula 2 shown in Table 7 below. The physical properties of the phosphor prepared above are shown in Table 7 and FIG.

EXPERIMENTAL EXAMPLE 1 Measurement of Particle Size Distribution (PSA) of Phosphor

9 shows the particle size distribution (PSA) of the blue light-emitting fluorescent substance of the present invention. At this time, Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue green light emitting phosphor was used, and the specific results are shown in Table 8 below.

From the above results, it was found that the blue-green light emitting phosphor of the present invention had a distribution (Dispersive, D10) of 1 to 10 탆, D20 of 5 to 15 탆, D30 of 10 to 20 탆, D40 of 10 to 25 탆, D60: 15 to 30 占 퐉, D70: 15 to 35 占 퐉, D80: 20 to 40 占 퐉, D90: 20 to 70 占 퐉, and D100: 25 to 100 占 퐉.

EXPERIMENTAL EXAMPLE 2 EDX analysis of phosphor

The blue-green light emitting phosphor of the present invention was analyzed (EDX) using an Energy Dispersive Spectrometer (Thermo, Noran).

Thus, as a result of EDX analysis, Wt% and At% for the components of the blue light-emitting fluorescent substance of the present invention are shown in Table 9, and the analysis results are shown in FIG.

From the results of Table 9, the elements of Ba, Mg, Si, O, N, F and Eu were confirmed by quantitative analysis of the blue light-emitting phosphor of the present invention by fluorescent X-ray analysis. More specifically, Wherein the element has a range of 20? Ba? 35, 1? Mg? 10, 25? Si? 45, 10? O? 20, 10? N? 20, 1? F? 10 and 0.1? Eu? It was confirmed that a phosphor having a total atomic percentage of 100% was produced. In addition, Ba, Mg, Si, O, N, F, Eu, K, P,

<Experimental Example 3> Color rendering index (CRI) measurement

Of the phosphors prepared above, Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 or The color rendering index (CRI) between the white LED device and the commercial LED device using the phosphor of Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 phosphor was measured.

The color rendering index (CRI) is a numerical value indicating how much the artificial light source shows the object color similar to the reference amount. The closer to the color rendering index 100, the better. The results are shown in Table 10 below.

As can be seen from Table 10, the commercial white LED device is a combination of a green phosphor of 520 to 560 nm and a red phosphor of 600 to 670 nm in a blue LED chip of 440 to 465 nm, and has a color temperature (CCT) of 2700 to 6500K (CRI) Ra > 90 &lt; / RTI &gt;

In addition, Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 or Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue green light emission of the present invention In the case of a white LED device using a phosphor, the color rendering index (CRI) Ra> 90 was achieved at a color temperature (CCT) of 2700 to 6500K.

In the current LED industry, the efficiency of the light flux is reduced by about 2 to 3% as the CRI is increased by 1 at a color temperature (CCT) of 2700 to 6500 K. However, the Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _{0.67 K 0.48 P 0.16 Li 0.67:} Eu 0.15 or _{Ba 5.32 Mg 0.53 Si 12.1 O 3.3} N 18.2 F 0.67 K 0.48 P 0.16 Li 0.67: Eu 0.15 cyan by using a light-emitting fluorescent substance, a light beam depending on the color rendering index (CRI) increased by one To 2%, and the portion of the light flux lowered is largely reduced, so that the light flux of the LED as a whole can be improved.

Specifically, when a white color is realized by a usual method of a green phosphor (Lu ₃ Al ₅ O ₁₂ : Ce) and a red phosphor (CaAlSiN ₃ : Eu), the color rendering index (CRI) increases from 80 to 90, CCT) is 2700 K to 6500 K, the luminous flux is reduced by 20 to 30% under the condition. In this case, when the luminous flux is 100% when the CRI is 80 and the CRI is 90, the luminous flux is about 70 to 80%.

On the other hand, the Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 or Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 cyan If the luminous phosphor is 100% when the CRI is 80 and the luminous flux is about 80 to 90% when the CRI is 90, the white phosphor can be produced by further containing the luminescent phosphor in the green phosphor and the red phosphor. And the luminous flux is improved to about 10%.

As a result, the white LED device containing the blue light-emitting phosphor of the present invention still retains the same CRI value as that of the commercial white LED device, and the light flux of 8.9 to 9.6 lm is increased by about 8%.

Therefore, the white LED device using the phosphor of the present invention improves the luminous intensity and the color rendering property by increasing the emission intensity of the LED by suppressing excessive use of the red phosphor component while relieving the portion where the red phosphor reduces the efficiency of some other phosphor .

Fig. 14 is a _graph showing the relationship between the light spectrum of the white LED device and the commercial white LED device fabricated using the Ba _2.84 Mg _0.11 Si _5.9 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue green light emitting phosphor of the present invention, (CRI) 90 under the 5000 K standard, and FIG. 15 is a graph showing the results of comparison of the white LEDs manufactured using Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 blue green light emitting phosphor of the present invention As a light spectrum observed with a color rendering index (CRI) of 80 in a 5000 K standard, the luminous flux rise result was confirmed.

As described above, the present invention provides a blue-green light-emitting fluorescent substance by an optimal combination of components of cation and anion and composition ratio thereof, and has excellent temperature characteristics as well as equivalent or excellent light emission characteristics as compared with commercial fluorescent substance products. Can be used for LED manufacturing.

In addition, in the white LED device produced by mixing the green phosphor and the red phosphor on the blue LED, the blue light-emitting phosphor of the present invention is further contained, so that the color reproducibility is 90 or more, It is possible to provide a white LED element having a remarkably high light intensity

Accordingly, the white LED device of the present invention is useful as a light source used in an illumination field selected from the group consisting of electronic parts of a display backlight, a head lamp for a vehicle, an interior light, a medical light source, a display light source, and an agricultural light source.

While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

102: LED lead frame
104: blue or UV chip
105, 106: wire
108 and 110: encapsulant such as epoxy or silicone
111: blue-green light-emitting phosphor
112: green or yellow light-emitting phosphor
113: Red light-emitting phosphor

Claims (13)

A blue-green light-emitting phosphor for a white light emitting diode element having a composition formula of the following formula (1)
Formula 1
A _a B _b O _c N _d C _e : RE _h
Wherein A is at least one or more elements selected from the group consisting of Be, Mg, Ca, Sr, Ba and Ra, B is at least one element selected from the group consisting of Si, Ge and Sn, C is C or Cl, F And Br, and RE is at least one or more elements selected from the group consisting of Eu, Ce, Sm, Er, Yb, Dy, Gd, Tm, Lu, Pr, Nd, Pm and Ho, 0 <b? 15, 0? C? 15, 0? D? 20, 0? E? 10, 0? H? 10. A blue-green light-emitting phosphor for a white light emitting diode element having a composition formula of the following formula (2)
(2)
A _a B _b O _c N _d C _e D _f e _g : RE _h
B is at least one or more elements of Si, Ge, and Sn; C is at least one element selected from the group consisting of C, Cl, F, Br E is at least one or more elements selected from the group consisting of P, As, Bi, Sc, Y and Lu, and RE is at least one element selected from the group consisting of Li, And 0 < c < 15, 0 < b < 15, and 0 < c < 15, 0 <d? 20, 0? E? 10, 0 <f? 10, 0 <g? 10, 0? The method of claim 1, wherein when the C element is any one of C, F, Cl, and Br, and 0.01? E? 10,
Ba _2.9 Si ₆ O ₃ N ₈ C _0.01 : Eu _0.1 , Ba _2.9 Si _5.9 O ₃ N ₈ C _0.1 : Eu _0.1, Ba _2.9 Si ₆ O ₃ N ₈ C ₁ : Eu _0.1 , Ba _2.9 Si ₆ O ₃ N _{8 C 5: Eu 0.1, Ba 2.9} Si 6 O 3 N 8 C 10: Eu 0.1, Ba 2.9 Si 6 O 3 N 8 F 0.01: Eu 0.1, Ba 2.95 Si 6 O 3 N 8 F 0.1: Eu 0.1, Ba 2.9 _{Si 6 O 3 N 8 F 1} : Eu 0.1, Ba 2.9 Si 6 O 3 N 8 F 5: Eu 0.1, Ba 2.9 Si 6 O 3 N 8 F 10: Eu 0.1, Ba 2.9 Si 6 O 3 N 8 Cl 0.01 : Eu _0.1 , Ba _2.95 Si ₆ O ₃ N ₈ Cl _0.1 : Eu _0.1, Ba _2.9 Si ₆ O ₃ N ₈ Cl ₁ : Eu _0.1 , Ba _2.9 Si ₆ O ₃ N ₈ Cl ₅ : Eu _0.1 , Ba _2.9 Si _{6 O 3 N 8 Cl 10: Eu} 0.1, Ba 2.9 Si 6 O 3 N 8 Br 0.01: Eu 0.1, Ba 2.95 Si 6 O 3 N 8 Br 0.1: Eu 0.1, Ba 2.9 Si 6 O 3 N 8 Br 1: Eu _{0.1, Ba 2.9 Si 6 O 3} N 8 Br 5: Eu 0.1 and _{Ba 2 .9 Si 6 O 3 N} 8 Br 10: a white light emitting diode elements, characterized in that one selected from the group consisting of Eu _{0 .1} Blue light emitting phosphor. The method according to claim 1, wherein Mg 0.01? A?? 1 is mixed with A element Ba and C element is mixed with F 0.01? E? 10,
Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 : Eu _0.15 , Ba _2.34 Mg _0.11 Si _5.45 O _2.89 N ₇ F _0.22 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 : Eu _0.15 , Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 : Eu _0.15 and Ba _11.55 Mg _1.3 Si _2.1 O _5.3 N _1.4 F _0.67 : Eu _0.15 . Wherein the blue light emitting phosphor is one selected from the group consisting of red, green and blue light emitting phosphors. The method according to claim 2, wherein Mg 0.01? A? 1 is added to the A element Ba, and the C element F has a D element of K 0.01? F? 10 and an E element of P 0.01? When incorporated,
Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.1 P _0.03 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.15 P _0.05 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.1 P _0.3 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K ₃ P ₁ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K _0.1 P _0.03 : Eu _0.15 , Ba _1.84 Mg _0.11 Si ₅ O _2.695 N _8.33 F _0.22 K _0.15 P _0.05 : Eu _0.15, Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K _0.3 P _0.1 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.22 K ₁ P ₃ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.2 K ₃ P ₁ : Eu _0.15 and Ba _2.79 Mg _0.11 Si ₆ O _3.62 N ₈ F _0.29 K _0.755 P _0.155 : Eu _0.1 . 5. A blue light emitting fluorescent substance for a white light emitting diode device, comprising: The method according to claim 2, wherein 0.01 ≦ a '≦ 1 is added to the A element Ba, 0.01 ≦ f ≦ 10 is satisfied for the D element Li and K, and P 0.01 ≦ g ≦ 10 Lt; / RTI &gt;&lt; RTI ID =
Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.32 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.72 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.145 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.7 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.395 N _7.93 F _0.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.64 N _7.93 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 , Ba _2.84 Mg _0.11 Si _5.95 O _3.4 N _8.33 F _0.22 K _0.5 P _0.1 Li _0.2 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.32 K _0.3 P _0.1 Li _0.1 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _0.72 K _0.3 P _0.1 Li _0.5 : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.395 N _8.6 F _1.22 K _0.3 P _0.1 Li ₁ : Eu _0.15 , Ba _1.84 Mg _0.11 Si _4.95 O _2.29 N _8.73 F _0.42 K _0.3 P _0.1 Li _0.2 : Eu _0.15 , Ba _2.79 Mg _0.11 Si ₆ O _3.62 N ₈ F _0.66 K _0.465 P _0.155 Li _0.66 : Eu _0.15 , Ba _5.32 Mg _0.53 Si _12.1 O _3.3 N _18.2 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 and Ba _11.55 Mg _1.3 Si _2.1 O _5.3 N _1.4 F _0.67 K _0.48 P _0.16 Li _0.67 : Eu _0.15 . 5. A blue light emitting fluorescent substance for a white light emitting diode element, comprising: The white light emitting diode device according to claim 1 or 2, wherein the phosphor has a wavelength range of 300 to 500 nm as an excitation source, emits an emission wavelength of 460 to 540 nm, and the emission center wavelength thereof is 490 to 510 nm. Blue light emitting phosphor. The phosphor according to claim 1 or 2, wherein the phosphor has a particle size distribution (PSA) of 1 to 10 mu m when D10, 10 to 30 mu m when D50, 20 to 70 mu m when D90 Of the blue light-emitting fluorescent substance for a white light emitting diode element. In a white LED device manufactured by mixing a green phosphor and a red phosphor on a blue LED,
A white LED device characterized by further comprising the blue-green light-emitting fluorescent substance according to any one of claims 1 to 6. 10. The phosphor according to claim 9, wherein a green phosphor, a red phosphor and a blue green light emitting phosphor are of a dispersive type; Conformal type; Or a remote type LED package according to the present invention. The white LED device according to claim 9, wherein 0.1 to 99 parts by weight of the blue-green light-emitting fluorescent material is contained in 100 parts by weight of silicon, epoxy resin or encapsulant. The white LED device according to claim 9, wherein the device has a color rendering index (CRI) of 65 to 98 at a color temperature (CCT) of 2700 to 6500K. The present invention is applied to any one of lighting fields selected from the group consisting of electronic parts fields of display backlight or head lamps for vehicles, indoor lamps, outdoor lamps, street lamps, election plate lights, stadium lights, medical light sources, exhibition light sources,
A light source comprising the white LED element of claim 9.

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