KR20190114133A - Garnet structure oxide phosphor, preparing method of the same, and its luminescent property - Google Patents

Abstract

The present invention relates to a garnet structure Y_2 LuCaGaAl_2SiO_12 phosphor, a manufacturing method of the garnet structure Y_2 LuCaGaAl_2SiO_12 phosphor, and luminescent properties of the garnet structure Y_2 LuCaGaAl_2SiO_12 phosphor.

Description

GARNET STRUCTURE OXIDE PHOSPHOR, PREPARING METHOD OF THE SAME, AND ITS LUMINESCENT PROPERTY}

The present application is directed to a garnet structure LuCaGaAl Y ₂ SiO ₂ phosphor _12, the garnet structure Y ₂ SiO ₂ LuCaGaAl production method of the phosphor _12, and the light emission properties of the garnet structure LuCaGaAl Y ₂ SiO _{2 12} phosphor.

There are many ways to implement white through light emitting diodes (LEDs), but the currently commercialized and commonly used method is to apply yellow phosphors to blue LEDs. The phosphor is widely used due to its easy manufacturing and low light loss because of its high light conversion efficiency.

For white LEDs using phosphors, YAG: Ce (yttrium aluminum garnet) phosphors are mainly used. However, a white LED using a YAG: Ce phosphor has a disadvantage in that color invariance is inferior, synthesis is possible only at very high temperatures, and a spectral band having a very narrow fluorescent excitation wavelength is formed.

[Preceding technical literature]

Republic of Korea Patent Publication No. 2014-0124041.

The present application is to provide a garnet structure oxide phosphor, a method of producing the garnet structure oxide phosphor, and the luminescence properties of the garnet structure oxide phosphor.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application provides a garnet structure oxide phosphor represented by the following Chemical Formula 1:

[Formula 1]

Y _2-x LuCaGaAl ₂ SiO ₁₂ : xLn ³⁺ ;

In Chemical Formula 1,

Ln is Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb,

0≤x≤0.5

A second aspect of the present application provides a method of preparing a garnet structure oxide phosphor represented by the following Chemical Formula 1 using a solid-state reaction method:

[Formula 1]

Y _2-x LuCaGaAl ₂ SiO ₁₂ : xLn ³⁺ ;

In Chemical Formula 1,

Ln is Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb,

0≤x≤0.5

According to embodiments herein, Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : xLn ^{3 +} (Ln = Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er) using a solid-state reaction method Or a novel garnet structure phosphor for a white-light emitting diode, which has not been reported so far, denoted as Yb) can be prepared.

The garnet structure phosphor according to the embodiments of the present invention can control the emission color by emitting yellow, red, or green, respectively, depending on the type of the rare earth metal ions to be doped, and have characteristics such as high brightness, high color purity, and high brightness. Therefore, it can be applied to a white light emitting diode device.

FIG. 1 shows an XRD pattern of Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : xTb ^{3 +} (0 ≦ _x ≦ 0.12) phosphors in one embodiment of the present application.
FIG. 2 shows excitation spectra of Y _2-x LuCaGaAl ₂ SiO ₁₂ : xTb ³⁺ (0.02 ≦ _x ≦ 0.12) phosphors observed at 545 nm in one embodiment of the present disclosure.
FIG. 3 shows emission spectra of Y _2-x LuCaGaAl ₂ SiO ₁₂ : xTb ³⁺ (0.02 ≦ _x ≦ 0.12) phosphors measured at 272 nm in an example of the present disclosure.
FIG. 4 illustrates a cross-relaxation mechanism of Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : xTb ^{3 +} (0.02 ≦ _x ≦ 0.12) phosphors in one embodiment of the present disclosure.
5 is Y ₂ when x is 0.02 (●), 0.04 (■), 0.06 (◆), 0.08 (▲), 0.10 (▼), and 0.12 (◀), respectively, in an embodiment of the present application. _{- x} LuCaGaAl ₂ SiO _12: shows the CIE coordinates of xTb ^{3 +} phosphor.
FIG. 6 shows an XRD pattern of Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : _x Ce ^{3 +} (0 ≦ _x ≦ 0.1) phosphors in one embodiment of the present application.
FIG. 7 shows excitation spectra of Y _2-x LuCaGaAl ₂ SiO ₁₂ : xCe ³⁺ (0.02 ≦ _x ≦ 0.1) phosphors measured at 505 nm in one embodiment of the present application.
8A to 8C show emission spectra of Y _2-x LuCaGaAl ₂ SiO ₁₂ : xCe ³⁺ (0 ≦ _x ≦ 0.1) phosphors under 435 nm excitation in one embodiment of the present application. _{, (b) Y 1.94 LuCaGaAl 2} SiO 12: deconvolution of the emission spectrum 0.06Ce ³⁺ phosphor, and _{(c) Y 1.94 LuCaGaAl 2 SiO} 12: an emission spectrum of a Ce ^{+ 3} fluorescent material: 0.06Ce ³⁺ phosphor and LuAG It is shown.
9 is Y _{2- x} LuCaGaAl ₂ SiO when x is 0.02 (●), 0.04 (■), 0.06 (◆), 0.08 (▲), and 0.10 (▼) in one embodiment of the present application. _12: shows the CIE coordinates of xCe ^{3 +} phosphor.
Figure 10 is, in one embodiment of the present application, Y _{2- x} LuCaGaAl SiO _{2 12:} shows the XRD pattern of xEu ^{+ 3} (0≤x≤0.12) phosphor.
FIG. 11 shows an excitation spectrum of a Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : xEu ^{3 +} (0.02 ≦ _x ≦ 0.12) phosphor in one embodiment of the present application.
Figure 12 is, in one embodiment of the present application, Y _{2- x} LuCaGaAl SiO _{2 12:} shows the emission spectrum of the xEu ^{+ 3} (0.02≤x≤0.12) phosphor.
13 is Y ₂ when x is 0.02 (●), 0.04 (■), 0.06 (◆), 0.08 (▲), 0.10 (▼), and 0.12 (◀), respectively, in one embodiment of the present application. _{- x} LuCaGaAl ₂ SiO _12: shows the CIE coordinates of the phosphors xEu ^{+ 3.}

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, "phosphor" means a material that absorbs various forms of energy and emits visible light energy due to the inherent energy difference of the material itself, and a general inorganic phosphor is a host lattice. ) And an activator in which impurities are mixed at an appropriate position, and the activator serves to determine the emission color by determining an energy level involved in the light emission process.

Throughout this specification, "garnet structure" means a structure that is generally configured as a structural formula of X ₃ Y ₂ Z ₃ O ₁₂ , wherein X is a dodecahedral site, Y is Octahedral site, Z is a tetrahedral site.

Throughout this specification, when a part is said to be "connected" with another part, this includes not only the "directly connected" but also the "electrically connected" between other elements in between. do.

Throughout this specification, when a member is located “on” another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated. As used throughout this specification, the terms “about”, “substantially”, and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the stated meanings are set forth, and the understandings herein Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term “step of” or “step of” does not mean “step for”.

Throughout this specification, the term “combination (s) thereof” included in the representation of a makushi form refers to one or more mixtures or combinations selected from the group consisting of components described in the representation of makushi form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.

Hereinafter, with reference to the accompanying drawings will be described embodiments and embodiments of the present application; However, the present disclosure may not be limited to these embodiments, examples, and drawings.

A first aspect of the present application provides a garnet structure oxide phosphor represented by the following Chemical Formula 1:

[Formula 1]

Y _2-x LuCaGaAl ₂ SiO ₁₂ : xLn ³⁺ ;

In Chemical Formula 1,

Ln is a rare earth element such as Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb,

0≤x≤0.5

In one embodiment of the present application, the garnet structure oxide phosphor may have a cubic garnet crystal structure.

In one embodiment of the present application, the garnet structure generally refers to a structure that is configured as a structural formula of X ₃ Y ₂ Z ₃ O ₁₂ , wherein X is a dodecahedral site, Y is octahedron Octahedral site, Z is a tetrahedral site], eg, Y _{2- x} LuCaGaAl ₂ SiO ₁₂ It may include a garnet structure.

In one embodiment of the present application, the garnet structure oxide phosphor may include light emission selected from the group consisting of yellow, red, green, and combinations thereof. For example, depending on the kinds of the rare earth metal ion of ^{Ce 3 +, Eu 3 +,} Tb 3 +, Dy 3 +, Sm 3 +, Ho 3 +, Pr 3 +, Er 3 +, or Yb ^{3 +} , Respectively, yellow, red, or green may emit light, and a combination of these may implement white light.

Since the garnet structure oxide phosphor according to the embodiment of the present application has high luminescence intensity, high color purity, high brightness, and the like, it may be suitably used as a phosphor for various displays such as LEDs, in particular, WLEDs.

A second aspect of the present application provides a method for preparing a garnet structure oxide phosphor, which is performed by a solid-state reaction method (solid phase method) and is represented by the following Chemical Formula 1:

[Formula 1]

Y _2-x LuCaGaAl ₂ SiO ₁₂ : xLn ³⁺ ;

In Chemical Formula 1,

Ln is a rare earth element such as Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb,

0≤x≤0.5

With respect to the method of manufacturing the garnet structure oxide phosphor according to the second aspect of the present application, detailed descriptions of portions overlapping with the first side of the present application have been omitted, but the contents described in the first aspect of the present application are omitted herein. The same can be applied to the second aspect of.

In one embodiment of the present application, the solid phase method is an oxide or carbonate of a metal selected from the group consisting of Y, Lu, Ca, Ga, Al, Si, and combinations thereof; And calcining in a temperature range of about 100 ° C. to about 1,000 ° C. by mixing oxides or carbonates such as Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb; And annealing the calcined powder in a temperature range of about 1,000 ° C. to about 2,000 ° C. to obtain a garnet structure phosphor, but may not be limited thereto.

In one embodiment of the present application, the solid phase method is the most common method of manufacturing a ceramic, by the solid phase method can easily and economically mass-produce the garnet structure oxide phosphor, but may not be limited thereto.

In one embodiment of the present application, the calcination step may be performed to remove impurities such as organic matter, the calcination may be performed at a temperature range of about 100 ℃ to about 1,000 ℃, but is not limited thereto. You may not. For example, the calcining may be about 100 ° C. to about 1,000 ° C., about 100 ° C. to about 800 ° C., about 100 ° C. to about 600 ° C., about 100 ° C. to about 400 ° C., about 100 ° C. to about 200 ° C., about 200 ° C. To about 1,000 ° C, about 200 ° C to about 800 ° C, about 200 ° C to about 600 ° C, about 200 ° C to about 400 ° C, about 400 ° C to about 1,000 ° C, about 400 ° C to about 800 ° C, about 400 ° C to about 600 ° C, about 600 ° C to about 1,000 ° C, about 600 ° C to about 800 ° C, about 800 ° C to about 1,000 ° C, or about 500 ° C to about 700 ° C, about 100 ° C to about 800 ° C, about 100 ° C to about 800 ℃, may be performed at a temperature range of about 100 ℃ to about 800 ℃, but may not be limited thereto.

In one embodiment of the present application, flux may be added after the calcination, but may not be limited thereto. For example, a small amount of flux may be added after the calcining, but may not be limited thereto.

In one embodiment of the present application, the flux may be in a liquid form having a melting point lower than the annealing temperature, it may be to serve as a carrier between the reactants, but may not be limited thereto.

In one embodiment of the present application, the flux does not remain in the final product, it may be to promote crystal growth of the product.

In one embodiment of the present application, the flux may be, for example, an alkali metal, an alkaline earth metal, or a halogen compound, for example, K ₂ CO ₃ , but may not be limited thereto.

In one embodiment of the present application, the heat treatment temperature may be lowered due to the flux, thereby reducing the cost of generating the phosphor, but may not be limited thereto.

In one embodiment of the present application, the annealing may be performed in a temperature range of about 1,000 ℃ to about 2,000 ℃, but may not be limited thereto. For example, when the annealing temperature is greater than about 2,000 ° C., the aggregation becomes severe, and when the annealing temperature is less than about 1,000 ° C., it may have a monoclinic crystal structure. Thus, the annealing may be performed at about 1,000 ° C. to about 2,000 ° C. It is preferably carried out in the temperature range.

In one embodiment of the invention, the annealing is about 1,000 ℃ to about 2,000 ℃, about 1,000 ℃ to about 1,800 ℃, about 1,000 ℃ to about 1,600 ℃, about 1,000 ℃ to about 1,400 ℃, about 1,000 ℃ to about 1,200 ℃ , About 1,200 ° C. to about 2,000 ° C., about 1,200 ° C. to about 1,800 ° C., about 1,200 ° C. to about 1,600 ° C., about 1,200 ° C. to about 1,400 ° C., about 1,400 ° C. to about 2,000 ° C., about 1,400 ° C. to about 1,800 ° C., about It may be carried out at a temperature range of 1,400 ℃ to about 1,600 ℃, about 1,600 ℃ to about 2,000 ℃, about 1,600 ℃ to about 1,800 ℃, about 1,800 ℃ to about 2,000 ℃, or about 1,500 ℃ to about 1,700 ℃, It may not be limited.

In one embodiment of the present application, the annealing is a process of synthesizing ceramic crystals, the active material may enter the mother lattice through the annealing, but may not be limited thereto.

In one embodiment of the present application, the garnet structure oxide phosphor may have a cubic crystal structure through the annealing, but may not be limited thereto.

Hereinafter, the present invention will be described in more detail with reference to examples of the present application, but the following examples are merely illustrated to aid the understanding of the present application, and the content of the present application is not limited to the following examples.

[ Example ]

Garnet  Preparation of Structured Oxide Phosphors

_{Y 2- x LuCaGaAl 2 SiO 12:} xLn (0≤x≤0.5, Ln = Ce 3 +, Eu 3 +, or Tb ^{3 +)} phosphors that were produced through a conventional method step. Starting materials used in the process were as follows: Y ₂ O ₃ (High Purity Chemical, 99.99%), Lu ₂ O ₃ (Chinalco Rare Earth Co. Ltd., 99.995%), CaCO ₃ (High Purity Chemical, 99 %), Ga ₂ O ₃ (High Purity Chemical, 99.9%), a-Al ₂ O ₃ (High Purity Chemical, 99.99%), SiO ₂ (High Purity Chemical, 99.9%), La ₂ O ₃ (High Purity Chemical , 99.99%), ZrO (NO ₃ ) ₂ (High Purity Chemical, 98%), Li ₂ CO ₃ (High Purity Chemical, 99%), Na ₂ CO ₃ (High Purity Chemical, 99%), K ₂ CO ₃ (High Purity Chemical, 99%), (NH ₄ ) ₂ HPO ₄ (Samchun Chemical, 99%). CeO ₂ (High Purity Chemical, 99.99%), Eu ₂ O ₃ (High Purity Chemical, 99.9%), and Tb ₄ O ₇ (High Purity Chemical, 99%).

First, Y ₂ O ₃ , Lu ₂ O ₃ , CaCO ₃ , Ga ₂ O ₃ , a-Al ₂ O ₃ , SiO ₂ , CeO ₂ , Eu ₂ O ₃ , and Tb ₄ O ₇ were weighed and weighed above The powder was mixed with acetone (5 mL) and the mixture was mixed homogeneously for 30 minutes using mortar and mortar. The mixed powder was transferred to an alumina crucible and calcined at 800 ° C. for 4 hours. A small amount of K ₂ CO ₃ flux (5% by weight) was added to the calcined powder. The resulting powder was annealed at 1,600 ° C. for 5 hours.

Garnet  Characterization of Structural Oxide Phosphors

)을 이용한 X-선 회절분석기 (XRD; Rigaku RINT2000, Japan)를 사용하여 분석되었다. 상기 형광체의 PL 스펙트럼은 제논 램프가 장착된 분광 형광 측정기 (FS-2, Scinco Co., Korea)를 사용하여 수득되었다. 모든 발광 스펙트럼은 동일한 양의 제조된 형광체를 사용하여 얻어지며 동일한 조건 하에서 기록되었다. CIE 계산기를 사용하여 관찰된 발광 스펙트럼으로부터 CIE (Commission Internationale de l' Eclairage) 색도 좌표 (x, y)가 계산되었다. 또한, CIE 좌표 (x, y) 데이터를 사용하여 상관 색온도 (CCT)와 색 순도가 계산되었다.The crystal structure of the prepared garnet structure oxide phosphor is Cu Kα line (α = 1.5406

And X-ray diffractometer (XRD; Rigaku RINT2000, Japan). The PL spectrum of the phosphor was obtained using a spectrofluorometer (FS-2, Scinco Co., Korea) equipped with a xenon lamp. All emission spectra were obtained using the same amount of prepared phosphor and were recorded under the same conditions. The Commission Internationale de l'Eclairage (CIE) chromaticity coordinates (x, y) were calculated from the emission spectra observed using the CIE calculator. In addition, correlation color temperature (CCT) and color purity were calculated using CIE coordinate (x, y) data.

Y as host material _{2- x} LuCaGaAl ₂ SiO ₁₂ of  Select

The herein, Y _{2- x} LuCaGaAl SiO _{2 12} is selected as the host material and Ce ^{3 +,} Eu ^{3 +} or ^{3 +} Tb The structure and properties of the PL-doped Y _{2- x} LuCaGaAl SiO _{2 12} phosphor was studied.

Example  1: Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : x Tb ^{3 +} (0 = x 0.12) phosphor

공간 그룹을 형성한다. 도 1의 XRD 패턴에서, 약한 피크들은 Ca₂Ga₂SiO₇ (JCPDS No. 74-1608), CaAl₂Si₂O₇ (JCPDS No. 74-1607), 및 YAlO₃ (JCPDS No. 28-0037)에 해당한다. 도핑된 Tb^{3 +} 이온은 상기 Y_{2- x}LuCaGaAl₂SiO₁₂의 결정 구조에 큰 영향을 미치지 않는다.1 is, Y _{2- x} LuCaGaAl doped with Tb ^{3 +} as a metal ion in _{2 SiO 12, Y 2-x} LuCaGaAl 2 SiO 12: xTb 3+ (0≤x≤0.12) shows the XRD pattern of the phosphor. YAG's standard JCPDS No. The Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : xTb ^{3 +} phosphor, consistent with 33-0040, has a cubic garnet structure and

Form a space group. In the XRD pattern of FIG. 1, the weak peaks are Ca ₂ Ga ₂ SiO ₇ (JCPDS No. 74-1608), CaAl ₂ Si ₂ O ₇ (JCPDS No. 74-1607), and YAlO ₃ (JCPDS No. 28-0037 Corresponds to). Doped Tb ^{3 +} ions do not have a significant impact on the crystal structure of the Y _{2- x} LuCaGaAl ₂ SiO _12.

The monitored at _{545 nm Y 2- x LuCaGaAl 2 SiO} 12: xTb excitation spectrum of ^{3 +} (0.02≤x≤0.12) is phosphor, Tb ^{3 +} ion of 4f ⁸ → 4f ⁷ by 234 nm due to the 5d transition ^1, Three broad bands were shown at 272 nm and 320 nm (FIG. 2). The weak peak observed at 356 nm, 374 nm, 380 nm and 489 nm, the Tb ^{3 +} ions are ⁷ F ₆ from a ground state ^{_{5 D 2, 5 L 10,}} 5 D 3 and ⁵ D ₄ each transition to the excited state It was consistent with that. 4f ⁸ → the Tb ^{3 +} ion 4f ⁷ 5d ¹ transition is equally acceptable to have stronger strength than the 4f ⁸ → 4f ⁸ transition. As the concentration of the Tb ^{3 +} increases, this profile was no significant difference, except for those of this strength. The excitation strength was gradually increased by doping Tb ^{3 +} ions to x = 10 mol%, and it was confirmed that the concentration of the Tb ^{3 +} ions decreased with further increase.

The emission spectrum of the Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : xTb ^{3 +} (0.02 ≦ _x ≦ 0.12) phosphor under 272 nm excitation is shown in FIG. 3. 384 nm, 418 nm, 438 nm , the peak observed at 470 nm is ⁵ D of ^{_{Tb 3 + 3 → 7 F j}} (j = 6-3) due to the transition, and, 489 nm, 545 nm, 592 nm, and 625 the peak observed in nm is due to the ^{_{5 D 4 → 7 F j (}} j = 6-3) transition of Tb ^{3 +.} Decreased the intensity of the peak caused by the ⁵ D ₃ → ⁷ F ₆ transition, as Tb ^{+ 3} concentration is increased to 10 mol%. This phenomenon is due to cross relaxation. ^Since the energy difference between ⁵ D ₃ and ⁵ D ₄ (5915 cm ^-1 ) is similar to the energy difference between ⁷ F ₆ and ⁷ F ₀ (6000 cm ^-1 ), the excitation energy is ⁵ D of Tb ^{3 +} ion in the _third level it may be a transition to the ground state and the adjacent Tb ^{3 +.} The cross relaxation phenomenon can be explained by the following equation (1):

A schematic energy level illustrating the possible cross-relaxation mechanism is shown in FIG. 4. Under 272 nm Here, Tb ^{3 +} ions are then excited 5d herein by state (step 1), the non-5d in this state to the ⁵ D ₃ levels in the ground state - is relaxed radioactive. Tb ^{3 +} ions can emit blue light due to a radioactive transition to a ⁷ F _{j (j} = 6-3) in the ground state ⁵ D ₃ levels (process 2). Further, the electrons of the ⁵ D ₃ levels in the ⁵ D ₄ level is non-radioactive and can be reached with (process 3), ⁷ F _j from the ⁵ D ₄ level (j = 6-3) Radiation transition to the ground state is possible (process 4), which corresponds to green light emission. When the Tb ^{3 +} ions are located close to each other, the resonance condition can be satisfied due to the small energy difference between ⁵ D ₃ → ⁵ D ₄ and ⁷ F ₆ → ⁷ F ₀ . The energy difference between ⁵ D ₃ and ⁵ D ₄ (5915 cm ⁻¹ ) is similar to the energy difference between ⁷ F ₆ and ⁷ F ₀ (6000 cm ⁻¹ ). At sufficiently high concentration of Tb ^{+ 3,} adjacent to Tb ^{+ 3} ions begin to interact with one another. The cross-relaxation occurs from the ⁵ D ₃ levels of a Tb ^{3 +} ion, because of energy transfer to the ground state of an adjacent Tb ³⁺ ions. Relaxation increases the emission intensity of green is increased the probability of electron transfer to a ⁷ F _{j (j} = 6-3) in the basal level ⁵ D ₄ level -, cross, as Tb ^{+ 3} concentration. As the Tb ^{3 +} concentration increases to 10 mol%, the intensity of the transition of ⁵ D ₄ → ⁷ F _j (j = 6-3) increases and then the luminescence intensity decreases due to concentration disappearance at higher Tb ^{3 +} concentrations. .

A CIE chromaticity diagram of the Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : xTb ^{3 +} (0.02 ≦ _x ≦ 0.12) phosphor is shown in FIG. 5. In the CIE diagram, the value of the x coordinate and the y coordinate is increased as Tb ^{+ 3} concentration. In addition, CCT and color purity of the Y _2-x LuCaGaAl ₂ SiO ₁₂ : xTb ³⁺ phosphor were calculated from the CIE coordinates (x, y), and the results are shown in Table 1.

Example  2: Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : x Ce ^{3 +} (0 = x 0.1) phosphor

공간 그룹을 가지고 있다. 상기 Y_{2- x}LuCaGaAl₂SiO₁₂:xCe^{3 +} (0.02≤x≤0.1) 형광체의 XRD 패턴은, 도핑되지 않은 Y₂LuCaGaAl₂SiO₁₂ 형광체의 패턴과 유사하였으며, 이것은 Ce^{3 +}가 Y₂LuCaGaAl₂SiO₁₂의 결정 구조에 영향을 미치지 않는다는 것을 나타낸다. Ca₂Ga₂SiO₇ (JCPDS No. 74-1608), CaAl₂Si₂O₇ (JCPDS No. 74-1607), 및 YAlO₃ (JCPDS No. 28-0037) 상이 2θ = 31.04°, 31.38° 및 32.02°에서 소량 검출되고 있다.6 is doped with different concentrations of Ce ^{+ 3,} Y _{2- x} LuCaGaAl SiO _{2 12:} shows the XRD pattern of xCe ^{3 +} phosphor. The _{Y 2- x LuCaGaAl 2 SiO 12:} XRD pattern of xCe ^{3 +} phosphor YAG of JCPDS No. It matched the pattern of 33-0040. The _{Y 2- x LuCaGaAl 2 SiO 12:} xCe 3 + phosphor has a cubic crystal structure and

It has a space group. The XRD pattern of the Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : _x Ce ^{3 +} (0.02 ≦ _x ≦ 0.1) phosphor is Y ₂ LuCaGaAl ₂ SiO ₁₂ , which is not doped. Was similar to the pattern of the phosphor, this indicates that Ce ^{3 +} does not affect the crystal structure of Y ₂ LuCaGaAl ₂ SiO _12. Ca ₂ Ga ₂ SiO ₇ (JCPDS No. 74-1608), CaAl ₂ Si ₂ O ₇ (JCPDS No. 74-1607), and YAlO ₃ (JCPDS No. 28-0037) phases 2θ = 31.04 °, 31.38 ° and Small amounts are detected at 32.02 °.

Figure 7, the _{Y 2- x LuCaGaAl 2 SiO 12:} xCe 3 + (0.02≤x≤0.1) shows the excitation spectrum of the phosphor. Excitation spectra ranging from 200 nm to 490 nm show two broad bands at 348 nm and 435 nm. The bands are present due to Ce ^{3 +} ions to transfer to the 4f ^{1 (2} F _5/2) 5d excited state _⁽² D ^_5/2 and _² D ^_3/2) in the ground state. The strongest band at 435 nm matched the emission wavelength of the blue LED chip, which allows the Y _2-x LuCaGaAl ₂ SiO ₁₂ : xCe ³⁺ (0.02 ≦ _x ≦ 0.1) phosphor to be effectively excited by the blue LED chip. Indicates. The Ce ^{+ 3} concentration was increased with increasing intensity is here to 6 mol%, where the intensity decreased as the concentration is increased to above.

The emission spectrum obtained under 435 nm excitation showed a wide asymmetric band with a maximum at 505 nm, which corresponds to green emission (Fig. 8 (a)). The green light emission is due to the transition of Ce ³⁺ ions from the 5d excited state to the 4f ( ² F _5/2 and ² F _7/2 ) ground states. The wide asymmetric region can be deconvolved into two Gaussian bands having maximum values at 499 nm and 538 nm, as shown in FIG. 8 (b). As shown in Fig. 8 (a), wherein Y _{2- x} LuCaGaAl ₂ SiO _12: emission intensity of xCe ^{3 +} (0.02≤x≤0.1) phosphor was increased as the Ce ^{+ 3} concentration is increased up to 6 mol%, Increasing beyond that, the emission intensity decreased due to the concentration quenching effect. In addition, Y in the _{505 nm 1.94 LuCaGaAl 2 SiO 12:} 0.06Ce 3+ emission intensity and commercial Lu ₃ Al ₅ O of the phosphor _{^{12: Ce 3 + (LuAG:}} Ce) also the strength thereof in order to compare the light intensity of the fluorescent substance 8 (c). Y _{1. 94} LuCaGaAl ₂ SiO ₁₂ in the 505 nm: 0.06Ce ³⁺ emission intensity of the phosphor is commercially _{Lu 3 Al 5 O 12: 71} % lower than the luminescence intensity of Ce ³⁺ phosphor.

CIE coordinates (x, y) is the Y _{2- x} LuCaGaAl ₂ SiO _12: it is useful to determine the light emission color and purity of the xCe ^{3 +} (0.02≤x≤0.1) phosphor. The CIE chromaticity coordinates (x, y) were calculated from the obtained luminescence data, and the results are shown in FIG. 9. All CIE coordinates (x, y) of the Y _2-x LuCaGaAl ₂ SiO ₁₂ : _x Ce ³⁺ (0.02 ≦ _x ≦ 0.1) phosphor were in the green region. When Ce ^{3 +} ion concentration is increased from 2 mol% to 10 mol%, it was changed to the CIE coordinates (x, y) is from (0.285, 0.544), (0.290, 0.550). In addition, the CCT and color purity of the Y _2-x LuCaGaAl ₂ SiO ₁₂ : _x Ce ³⁺ (0.02 ≦ _x ≦ 0.1) phosphor were calculated using CIE coordinates (x, y), and the results are shown in Table 2. .

Example  3: Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : x Eu ^{3 +} (0≤ x ≤0.12) phosphor

공간 그룹을 가지고 있음을 의미한다. 상기 도핑된 Eu^{3 +} 이온은 Y_{2- x} LuCaGaAl₂SiO₁₂:xEu³⁺ (0.02≤x≤0.12) 형광체의 결정 구조에 영향을 미치지 않았다.Next, Y _{2- x} LuCaGaAl SiO ₂ of ₁₂ doped with Eu ^{3 +} as a metal ion in the Y _{2- x} LuCaGaAl SiO _{2 12:} 10 the XRD pattern of x Eu ³⁺ (0≤x≤0.12) fluorescent Shown in All diffraction peaks were obtained from JCPDS No. 33-0040, which is consistent with the cubic crystal structure of Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : x Eu ³⁺

It means you have a group of spaces. The doped Eu ^{3 +} ion is _{Y 2- x LuCaGaAl 2 SiO 12:} x Eu 3+ (0.02≤x≤0.12) did not affect the crystal structure of the phosphor.

The _{Y 2- x LuCaGaAl 2 SiO 12:} x Eu 3 + (0.02≤x≤0.12) shows the excitation spectrum of the phosphor in Fig. This spectrum showed a wide band at 200 nm to 350 nm, which is due to electron transfer from Eu ^{3 +} O ^2-. The band position was slightly shifted towards longer wavelengths as the Eu ^{3 +} concentration. This is because increase in the bond lengths between Eu ^{3 +,} and O ^2-. The emission spectrum is shown a number of sharp peaks in the 300 nm to 550 nm range, which is due to 4f-4f transition of Eu ^{3 +} ions. The sharp peaks at 322 nm, 365 nm, 384 nm, 397 nm, 417 nm, 467 nm, and 530 nm are ⁷ F ₀ → ⁵ H ₅ , ⁷ F ₀ → ⁵ D ₄ , ⁷ F of Eu ³⁺ ions, respectively. ₀ → ⁵ L ₇ , ⁷ F ₀ → ⁵ L ₆ , ⁷ F ₀ → ⁵ D ₃ , ⁷ F ₀ → ⁵ D ₂ , ⁷ F ₀ → ⁵ D ₁ . ^There is the strongest peak at 395 nm because of the ⁷ F ₀ → ⁵ L ₆ transition, which coincides with the emission wavelength of the near ultraviolet LED chip. These results are the _{Y 2- x LuCaGaAl 2 SiO 12:} x Eu 3 + (0.02≤x≤0.12) indicates that the fluorescent material may be used as a near-ultraviolet red phosphor for a white LED.

12 is under 397 nm where the Y _{2- x} LuCaGaAl SiO _{2 12:} shows the emission spectrum of Eu ^{3 +} x (0.02≤x≤0.12) phosphor. Eu ^{3 +} ions in the ⁵ D ₀ → ⁷ because F _{j (j} = 1 to 4) transfer the light emission peak at 593 nm, 611 nm, 650 nm and 710 nm was observed. The strongest emission peak at 593 nm corresponds to yellow light emission and is due to the transition ⁵ D ₀ → ⁷ F ₁ . According to the Judd-Ofelt theory, magnetic dipole transitions ( ⁵ D ₀ → ⁷ F ₁ ) are allowed, and electric dipole transitions ( ⁵ D ₀ → ⁷ F ₂ ) are prohibited. Therefore, the light emission spectrum is predominantly by the ⁵ D ₀ → ⁷ F ₁ transition than the transition ⁵ D ₀ → ⁷ F _2. The Eu ^{3 +} concentration increases due to the increase of the emission intensity after up to 10 mol%, when Eu ^{3 +} concentration is increased beyond that concentration quenching decreases the emission intensity as. The concentration quenching is related to the non-radiative energy transfer between adjacent Eu ^{3 +} ions. As the Eu ^{3 +} ion doping concentration is increased, when the reduced average distance between adjacent Eu ^{3 +} ions, Eu ^{3 +} concentration exceeds a critical concentration, it takes place the non-personal relaxation, thereby the emission intensity is reduced accordingly.

13 is the Y _{2- x} LuCaGaAl ₂ SiO _12: illustrates a CIE chromaticity of x Eu ^{3 +} (0.02≤x≤0.12) phosphor. The calculated CIE, CCT, ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) values and color purity are shown in Table 2. All CIE coordinates (x, y) are in the yellow-red region. Eu ^{3 +} concentration was the value of the x and y coordinates as to increase from 2 mol% to 10 mol% change, CCT values were increased from 1750K to 1896K. The color purity values as Eu ^{3 +} concentration increased from 2 mol% to 10 mol% increased from 76.6% to 82.5%. ⁵ D ₀ → ⁷ F ₁ and ⁵ D ₀ → ⁷ F ₂ transition is the _{Y 2- x LuCaGaAl 2 SiO 12:} x Eu 3+ (0.02≤x≤0.12) environment around the Eu ^{3 +} ions in the emission spectrum of the phosphor It is important because it represents. Eu ^{3 +} ions of the crystal field strength around affects the electric dipole transition ⁵ D ₀ → ⁷ F _2. On the other hand, a magnetic dipole D ₀ → ⁷ F ₁ transition ⁵ does not substantially affected by the crystal field strength of Eu ^{3 +} ions around. In the case of the Y _{2- x} LuCaGaAl ₂ SiO ₁₂ : x Eu ³⁺ (0.02 ≦ _x ≦ 0.12) phosphor, the integration of luminescence intensity by ( ⁵ D ₀ → ⁷ F ₁ ) and ( ⁵ D ₀ → ⁷ F ₂ ) The value ratio, ie, the value ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ), was calculated. The calculated ratio is shown in Table 3, and the ratio was 0.85 to 0.96.

In this embodiment, the rare earth metal ions (Ce ^{+ 3,} Eu ^{+ 3} or ^{3 +} Tb) doped novel garnet Y _{2- x} LuCaGaAl SiO _{2 12} and a phosphor was prepared by a conventional method. Ce ^{3 +,} Eu ^{3 +} or ^{3 +} Tb-doped Y _2-x SiO ₂ LuCaGaAl crystal structure of the phosphor ₁₂ and PL properties were first investigated. The novel oxide garnet structure phosphor is Ce ^{3 +,} Eu ^{3 +,} or by the addition of Tb ^{3 +} ion, and each emitting yellow, red, or green, is a promising phosphor which may be applied to the white LED.

The foregoing description of the application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

Claims (5)

Garnet structure oxide phosphor represented by the following general formula (1):
[Formula 1]
Y _2-x LuCaGaAl ₂ SiO ₁₂ : xLn ³⁺ ;
In Chemical Formula 1,
Ln is Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb,
0≤x≤0.5
The method of claim 1,
The garnet structure oxide phosphor has a cubic garnet crystal structure.
The method of claim 1,
Wherein the garnet structure oxide phosphor includes yellow, red, or green light emission.
Method for producing a garnet structure oxide phosphor represented by the following general formula (1) using a solid-state reaction method:
[Formula 1]
Y _2-x LuCaGaAl ₂ SiO ₁₂ : xLn ³⁺ ;
In Chemical Formula 1,
Ln is Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb,
0 ≦ x ≦ 0.5.
The method of claim 4, wherein
The solid state method,
Oxides or carbonates of metals selected from the group consisting of Y, Lu, Ca, Ga, Al, Si, and combinations thereof; And calcining in a temperature range of 100 ° C. to 1,000 ° C. by mixing an oxide or carbonate of Ce, Eu, Tb, Dy, Sm, Ho, Pr, Er, or Yb; And
Annealing the calcined powder in a temperature range of 1,000 ° C. to 2,000 ° C. to obtain a garnet structure oxide phosphor.
Method for producing garnet structure oxide phosphor.

Images