KR20040096306A - Luminescence conversion light emitting diode comprising the sialon-based phosphors - Google Patents
Luminescence conversion light emitting diode comprising the sialon-based phosphors Download PDFInfo
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Abstract
Description
본 발명은 시알론 형광체 및 이를 포함하는 발광다이오드에 관한 것이다. 보다 상세하게는 본 발명은 발광다이오드(LED)를 여기원으로 사용하여 형광체를 발광시킴으로써 백색광, 혹은 상용이 가능한 발광색을 방출하는 발광 LED 소자를 제작하는 것 즉, 가시광(visible light)영역이나 근자외선 스펙트럼(near UV spectrum) 범위에서 방출되는 광원에 의해 여기 되어 오렌지색을 발광하는 시알론 형광체 및 이를 포함하면서 자체에서 청색을 발광하는 LED와의 혼합에 의해 백색광을 방출하는 발광다이오드에 관한 것이다. 특히, 시알론 형광체는 활성이온을 둘러싼 임자결정의 공유결합정도가 높아, 여기 및 발광 스펙트럼이 낮은 에너지(red-shift)쪽으로의 전이가 발생하여 고체발광소자의 제작에 크게 기여할 수 있다. 이 때 발광 스펙트럼은 사용된 활성제의 농도에 의존하기 때문에 색재현의 응용성이 뛰어나다. 에너지 발광다이오드(LED)에서 1차적으로 방출되는 광자(photon)와 이들에 의해 LED에 도포된 형광체를 여기 시켜 발생되는 2차광의 결합으로 원하는 색을 얻는 구조이다. 이때 사용되는 형광체가 시알론 (Sialon)계열 형광체이며, 이는 티오갈레이트(thiogallate), 알루미네이트(aluminate)계열 형광체 혹은 실리케이트(silicate)계열 형광체와 혼합하여 사용할 수도 있다.The present invention relates to a sialon phosphor and a light emitting diode comprising the same. More specifically, the present invention uses a light emitting diode (LED) as an excitation source to produce a light emitting LED device that emits white light or a commercially available light emission color by emitting a phosphor, that is, a visible light region or near ultraviolet light The present invention relates to a sialon phosphor that is excited by a light source emitted in the near UV spectrum and emits an orange color, and a light emitting diode that emits white light by mixing with an LED emitting blue light in itself. In particular, the sialon phosphor has a high degree of covalent bonding of the crystals surrounding the active ions, and thus, excitation and emission spectra may be shifted toward red-shift, which may greatly contribute to the fabrication of a solid light emitting device. At this time, since the emission spectrum depends on the concentration of the active agent used, the application of color reproduction is excellent. It is a structure that obtains a desired color by combining a photon emitted primarily from an energy light emitting diode (LED) and secondary light generated by exciting a phosphor coated on the LED by the photon. At this time, the phosphor used is a sialon-based phosphor, which may be mixed with thiogallate, aluminate-based phosphor, or silicate-based phosphor.
백색광을 방출하는 발광 변환 발광다이오드(luminescence conversion LED)는 현재 대략 460㎚ 영역의 파장을 가지는 청색 Ga(In)N 발광다이오드와 황색광을 방출하는 YAG:Ce3+인광물질(미합중국 특허 제5,998,925호와 유럽특허 제862,794호)의 결합으로 만들어진다. 그러나, 이러한 백색광 발광다이오드는 범용 조명용으로 단지 제한된 범위 내에서만 사용되는데, 이는 색 성분의 부재(주로 적색광 성분)로 인해 연색성(color rendering)이 나빠지기 때문이다. 대체 방법은 적색, 녹색, 청색 삼색을 섞어서 백색광이 나오게 하는 방법(예를 들면, 국제특허공개공보 WO 98/39805호를 참조)과 청색 LED위에 녹색, 적색을 섞어서 백색광이 나오게 하는 방법이 있다.Luminescence conversion LEDs emitting white light currently present blue Ga (In) N light emitting diodes having wavelengths in the region of approximately 460 nm and YAG: Ce 3+ phosphors emitting yellow light (US Pat. No. 5,998,925). And European Patent No. 862,794). However, such white light emitting diodes are used only within a limited range for general purpose illumination, because of the lack of color components (mainly red light components), resulting in poor color rendering. Alternative methods include mixing red, green, and blue colors to produce white light (see, for example, WO 98/39805) and mixing green and red on blue LEDs to produce white light.
백색 발광다이오드를 위한 해결책으로 특히 적녹청(RGB) 접근법, 다른 말로 하면적색, 녹색, 청색 삼색의 혼합에 의한 접근 방법과 황청(OG)접근법, 즉, 황색과 녹색을 이용한 접근 방법등이 이용될 수 있다. 적녹청(RGB) 접근법은 적색, 녹색, 청색의 LED들을 적절히 조합하여 백색광을 생성하는 방법이다. 이들 방법은 개별적으로 성능 및 제조방법이 최적화된 LED들을 사용하기 때문에 우수한 색 랜더링(Color rendering)을 얻을 수 있는 장점이 있는 반면에 구동조건의 조정이 난이하고, 여러 개의 LED들을 조합하여야 하기 때문에 제조가격이 매우 높다는 단점이 있다. 이 같은 어려움을 극복하기 위한 방법으로서 LED에 형광체를 도포하여 형광체로부터 발광하는 2차 광원을 이용하는 방법으로 대표적인 방법이 일본국 소재 니찌아사에서 개발한 청색 LED에 오렌지색을 내는 YAG:Ce형광체를 도포하여 백색광을 얻는 방식이다(미합중국 특허 제6,069,440호). 이 같은 방식은 2차광을 이용하면서 발생하는 양자결손(quantum deficits) 및 재방사효율에 기인한 효율이 감소하고, 색 랜더링이 용이하지 않다는 단점에도 불구하고 구동이 용이하고 가격이 현저히 저렴하다는 이점 때문에 널리 상용화되어 있다. 또한, 기존에 생산되고 있는 황색과 청색 LED를 이용한 백색 발광다이오드의 경우, 연색성 등의 문제로 조명용으로서의 한계가 있는 것이 사실이다. 이를 위해 가장 시급히 해결되어야 할 문제 중의 하나가 근자외선(380 내지 430㎚)영역과 가시광(450 내지 480㎚)영역에서 에너지를 흡수하여 가시광 영역의 광자를 방출할 수 있는 형광체를 개발하는 것이다.Solutions for white light-emitting diodes in particular include the red cyan (RGB) approach, in other words the approach of a mixture of red, green and blue tricolor and the yellow (OG) approach, ie the approach using yellow and green. Can be. The red cyan approach is a method of properly combining red, green and blue LEDs to produce white light. These methods have the advantage of obtaining excellent color rendering because they use LEDs that are individually optimized for performance and fabrication, while the driving conditions are difficult to adjust and the combination of multiple LEDs is required. The disadvantage is that the price is very high. As a method of overcoming these difficulties, a method of using a secondary light source that emits light from the phosphor by applying a phosphor to the LED is a representative method of applying a YAG: Ce phosphor having orange color to a blue LED developed by Nichia Corporation, Japan. To obtain white light (US Pat. No. 6,069,440). This method reduces the efficiency due to quantum deficits and re-radiation efficiency caused by the use of secondary light, and because of the advantages that it is easy to drive and the price is significantly lower despite the disadvantage that color rendering is not easy. It is widely commercialized. In addition, it is true that the white light emitting diodes using yellow and blue LEDs, which are produced in the past, have limitations for lighting due to problems such as color rendering. One of the most urgent problems to be solved is to develop a phosphor capable of absorbing energy in the near ultraviolet (380 to 430 nm) region and the visible light (450 to 480 nm) region to emit photons in the visible region.
본 발명의 목적은 근자외선 스펙트럼(near UV spectrum)과 청색범위에서 방출되는광원에 의해 여기 되어 가시광을 방출하는 시알론 형광체를 이용하여 발광변환 다이오드를 제공하는데 있다. 또한 시알론 형광체의 조성변환을 통해 1차적으로 사용된 LED에 가장 적합하도록 여기 및 발광 스펙트럼이 조정된 시알론 형광체를 제공하는데 있다.An object of the present invention is to provide a light emitting diode using a sialon phosphor which is excited by a near UV spectrum and a light source emitted in a blue range and emits visible light. In addition, the present invention provides a sialon phosphor whose excitation and emission spectra are adjusted to be most suitable for an LED used primarily through composition conversion of the sialon phosphor.
도 1은 본 발명의 하나의 실시예에 따른 시알론 형광체의 여기스펙트럼(도 1a)과 발광스펙트럼(도 1b)이다.1 is an excitation spectrum (FIG. 1A) and a light emission spectrum (FIG. 1B) of a sialon phosphor according to an embodiment of the present invention.
도 2는 본 발명의 다른 하나의 실시예에 따른 시알론 형광체의 여기스펙트럼(도 2a)과 발광스펙트럼(도 2b)이다.2 is an excitation spectrum (FIG. 2A) and a light emission spectrum (FIG. 2B) of a sialon phosphor according to another embodiment of the present invention.
도 3는 다른 하나의 실시예에 따른 시알론 형광체의 여기스펙트럼과 발광스펙트럼을 표시한 그림이다.3 is a diagram showing an excitation spectrum and a light emission spectrum of a sialon phosphor according to another embodiment.
본 발명에 따른 시알론 형광체는, 하기 화학식 1로 표시되는 평균지름이 10㎛ 미만의 크기를 갖는 분말형 화합물이다;The sialon phosphor according to the present invention is a powdery compound having an average diameter of less than 10 μm represented by the following formula (1);
상기 식에서, M은 마그네슘(Mg), 칼슘(Ca), 스트론튬(Sr), 바륨(Ba), 혹은 스칸디윰(Sc), 이트리윰(Y), 및 란타니윰(La)에서 선택되는 적어도 하나의 원소이고, R은 시알론 세라믹구조에 활성제(activator)로 들어갈 수 있는 유로피윰(Eu), 터비윰(Tb), 프라세오디뮴(Pr), 망간(Mn)들로 이루어지는 그룹으로부터 선택되는 적어도 하나의 원소이고, v는 금속원소 M의 원자가로서 2 또는 3의 정수이고, m, n 모두는 0 부터 12까지의 실수이고, x는 금속원자 M을 대체하는 활성제의 분율을 표시하며 그 범위는 0≤x≤1 이다.Wherein M is at least one selected from magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or scandicin (Sc), yttrium (Y), and lanthanum (La) R is at least one selected from the group consisting of europium (Eu), turbium (Tb), praseodymium (Pr), and manganese (Mn), which may enter an activator into the sialon ceramic structure. Element, v is the valence of the metal element M and is an integer of 2 or 3, m and n are all real numbers from 0 to 12, x is the fraction of the activator replacing the metal atom M, with a range of 0 ≦ x≤1.
바람직하게는 알파-시알론(α-sialon)을 형성하도록 m과 n이 1≤m≤3, 0≤n≤2 영역 이내의 실수가 될 수 있다.Preferably m and n may be real numbers within the range 1 ≦ m ≦ 3 and 0 ≦ n ≦ 2 to form alpha-sialon.
본 발명에 따른 시알론 형광체를 포함하는 발광다이오드는, 통상의 다이오드를 1차광원으로 이용하여 상기 화학식 1의 형광체를 여기시켜 발광되도록 상기 다이오드에 상기 화학식 1의 형광체를 인접하게 위치하도록 조합하여 이루어진다.The light emitting diode including the sialon phosphor according to the present invention is formed by combining the phosphor of Chemical Formula 1 adjacent to the diode to excite the phosphor of Chemical Formula 1 using a conventional diode as a primary light source. .
본 발명에 따른 시알론 형광체를 포함하는 백색광 발광다이오드는, 350 내지 480㎚영역에서 발광하는 다이오드를 1차광원으로 이용하여 상기 화학식 1의 형광체를 여기시키고, 이로부터 발광하는 오렌지색의 2차광과 1차광 자체와의 조합에 의해 백색광을 방출시키도록 이루어진다. 시알론 형광체의 흡수 스펙트럼은 350㎚에서 500㎚까지 넓게 분포하고 있어 근자외선 LED를 사용하여 백색광을 방출하는 것이 가능하다. 즉, 근자외선 LED에서 방출하는 1차광과 시알론 형광체, 녹색과 청색을 발광하는 스트론튬알루미늄을 혼합 또는 인접하게 위치하도록 조합하여 상기 2차광들의 조합에 의한 백색광을 방출시키도록 이루어진다.The white light emitting diode including the sialon phosphor according to the present invention excites the phosphor of Chemical Formula 1 by using a diode emitting light in a region of 350 to 480 nm as a primary light source, and emits orange secondary light and 1 that emit light therefrom. It is made to emit white light by combination with shading itself. The absorption spectrum of the sialon phosphor is widely distributed from 350 nm to 500 nm, and it is possible to emit white light using a near-ultraviolet LED. That is, the primary light emitted from the near-ultraviolet LED, the sialon phosphor, and the strontium aluminum emitting green and blue are mixed or adjacently positioned to emit white light by the combination of the secondary lights.
이하, 본 발명의 구체적인 실시예를 첨부한 도면을 참조하여 상세히 설명한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명에 따른 시알론 형광체는, 하기 화학식 1로 표시되는 평균지름이 10㎛ 미만의 크기를 갖는 분말형 화합물임을 특징으로 한다;The sialon phosphor according to the present invention is characterized in that the average diameter represented by the formula (1) is a powdery compound having a size of less than 10㎛;
화학식 1Formula 1
Mv m(1-x)/v·Si12-(m+n)·Alm+n·On·N16-n:Rmx/v M v m (1-x) / v · Si 12- (m + n) · Al m + n · O n · N 16-n: R mx / v
상기 식에서, M은 마그네슘(Mg), 칼슘(Ca), 스트론튬(Sr), 바륨(Ba), 혹은 스칸디윰(Sc), 이트리윰(Y), 및 란타니윰(La)에서 선택되는 적어도 하나의 원소이고, R은 시알론 세라믹구조에 활성제(activator)로 들어갈 수 있는 유로피윰(Eu), 터비윰(Tb), 프라세오디뮴(Pr), 망간(Mn)들로 이루어지는 그룹으로부터 선택되는적어도 하나의 원소이고, v는 금속원소 M의 원자가로서 2 또는 3의 정수이고, m, n 모두는 0 내지 12의 실수이고, x는 금속원자 M을 대체하는 활성제의 분율을 표시하며 그 범위는 0≤x≤1 이다. 상기 화학식에서 v는 금속원소 M의 원자가를 표시하였기 때문에 Mg, Ca, Sr, Ba의 경우는 2이며, Sc, Y, La는 3을 표시한다. m 은 시알론 구조에서 Si-N 결합이 Al-N결합으로 대체되는 정도를 나타내며 n은 Si-N결합이 Al-O결합으로 대체되는 정도를 표시하였기 때문에 m, n 모두는 0에서 12까지의 숫자를 취할 수 있지만, 바람직하게는 알파-시알론을 형성하는 1≤m≤3, 0≤n≤2 영역이 좋다. m은 1≤m≤3을 만족하고, n은 0≤n≤2을 만족하는 조건은 상 평형도에서 α-시알론을 형성하는 영역으로 표현되는 구조를 형성한다(참고문헌:J. Am. Ceram. Soc., 1991,74,2547). 활성제로 기능하는 R은 시알론 구조에서 M의 일부를 대체하는 구조를 갖는다.Wherein M is at least one selected from magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or scandicin (Sc), yttrium (Y), and lanthanum (La) And R is at least one selected from the group consisting of europium (Eu), turbium (Tb), praseodymium (Pr) and manganese (Mn), which can enter the sialon ceramic structure as an activator. Element, v is the valence of the metal element M and is an integer of 2 or 3, both m and n are real numbers from 0 to 12, x represents the fraction of the activator replacing the metal atom M and the range is 0 ≦ x ≤1. In the above formula, since v represents the valence of the metal element M, M is 2 for Mg, Ca, Sr, and Ba, and Sc, Y, and La are 3. m represents the extent to which Si-N bonds are replaced by Al-N bonds in the sialon structure, and n indicates the extent to which Si-N bonds are replaced by Al-O bonds. Although numbers can be taken, preferably 1 ≦ m ≦ 3, 0 ≦ n ≦ 2 areas forming alpha-sialon are preferred. m satisfies 1 ≦ m ≦ 3 and n satisfies 0 ≦ n ≦ 2 to form a structure represented by a region forming α-sialon in the phase balance (see J. Am. Ceram. Soc., 1991,74,2547). R, which functions as an activator, has a structure that replaces a portion of M in the sialon structure.
본 발명에 따른 형광물질들이 높은 연색성의 백색광 발광다이오드 제조에 사용되는 것은 매우 유리하다. 이 목적을 위해 형광 물질들은 서로 분리되거나 또는 혼합되어서 적용되고, 만약 적당하다면, 가능한 투명한 바인더로 결합된다(유럽 특허 제 862,794호). 형광물질들은, 320 내지 500㎚ 영역에서 흡수스펙트럼을 가지고 있으며 원하는 색상 로커스를 가지는 전체적인 가시광 방출이 형성될 만큼 충분히 넓은 영역(특히 적색의 비율이 높은)의 스펙트럼을 가지고 있어 색상 로커스는 넓은 범위 안에서 정해질 수 있다.It is very advantageous for the fluorescent materials according to the invention to be used for the production of high color rendering white light emitting diodes. For this purpose the fluorescent materials are applied separately or mixed together and, if appropriate, combined with a transparent binder as possible (European Patent No. 862,794). Phosphors have an absorption spectrum in the 320 to 500 nm range and have a broad spectrum (especially a high proportion of red) that is broad enough to form an overall visible light emission with the desired color locus, so that the color locus is defined within a wide range. Can be done.
상기한 바의 본 발명에 따른 발광다이오드는 백색광을 방출하는 조명기구의 개발과 연결하면 특히 유리하다. 이 조명기구는 발광다이오드 어레이 또는 각각의 발광다이오드들에 기반을 두고 있는 조명기구이거나, 인광물질들이 직접적으로 혹은 간접적으로 칩과 접촉하고 있는, 다시 말하면 칩에 직접적으로 사용되거나, 칩을 둘러싸고 있는 합성수지에 내장되어 있는, 직접 발광 변환 발광다이오드 조명기구로 구성될 수 있다.The light emitting diode according to the present invention as described above is particularly advantageous in connection with the development of a luminaire that emits white light. The luminaire is a light emitting diode array or a luminaire based on each of the light emitting diodes or the synthetic resin which phosphors are directly or indirectly in contact with the chip, ie used directly on the chip or surrounding the chip. It can be configured as a direct-emitting conversion light emitting diode lighting fixture, which is built in.
본 발명은 통상적으로 사용되는 청색 LED와 YAG:Ce형광체를 이용한 백색LED와는 달리 비-YAG:Ce형광체를 사용하는 것을 특징으로 한다. 본 발광시스템은 기존의 통상적인 백색LED에 대하여 향상된 성능을 나타낸다.The present invention is characterized by using a non-YAG: Ce phosphor, unlike a blue LED and a white LED using a YAG: Ce phosphor. The light emitting system exhibits improved performance over existing conventional white LEDs.
이하에서 본 발명의 바람직한 실시예 및 비교예들이 기술되어질 것이다. 이하의 실시 예들은 본 발명을 예증하기 위한 것으로서 본 발명의 범위를 국한시키는 것으로 이해되어져서는 안 될 것이다.Hereinafter, preferred embodiments and comparative examples of the present invention will be described. The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.
실시예 1(Ca-Si-AL-O-N 계 시알론 형광체/활성제:유로퓸 이온)Example 1 (Ca-Si-AL-O-N-based sialon phosphor / activator: europium ion)
본 발명에 따른 형광체로서 칼슘과 유로퓸이 도핑된 시알론 형광체를 합성하였다. 활성제로서 사용되는 유로퓸의 칼슘에 대한 혼합비율에 따라 여기 스펙트럼과 발광색을 변화시킬 수 있었으며, 열처리 조건과 조성변화를 통해 발광되는 광의 빛을 조절하였다.As the phosphor according to the present invention, a sialon phosphor doped with calcium and europium was synthesized. According to the mixing ratio of europium used as an activator to the calcium, the excitation spectrum and the emission color could be changed, and the light of the emitted light was controlled through the heat treatment conditions and the composition change.
위 형광체의 합성은 다음과 같은 방식을 따른다.Synthesis of the above phosphors follows the following manner.
원료(raw materials)로 α-Si3N4, AlN, CaCO3, Eu2O3가 사용되었으며, 고체용액을 형성하는 영역(참고문헌:J. Am.Ceram. Soc., 1991,74,2547)에서 측량하여 열처리되었다. 본 예는 Si3N4-Eu2O3:9AlN 라인에서 m=1.5, n=0.75가 선택되었다. 원료를 상기비율로 혼합하여 비수용성 용매, 예를 들면 핵산에서 볼밀법을 통해 24시간 밀링하였다. 이를 통해 나온 분체를 질소분위기에서 1,500 내지 1,900℃ 사이에서 2 내지 8시간 동안 열처리를 하였다. 이를 통해 제조된 물질을 다시 볼밀법을 통해 분쇄시킨 후, 1,000 내지 1,500℃ 사이에서 다시 2 내지 8시간 동안 환원분위기에서 2차 열처리를 하여 소정의 형광체를 수득하였다. 합성된 형광체의 광발광(PL) 스펙트럼을 도 1에 나타내었다. 도 1의 (a)는 여기 스펙트럼이고, (b)는 발광스펙트럼이다.Α-Si 3 N 4 , AlN, CaCO 3 , Eu 2 O 3 were used as raw materials, and the area for forming a solid solution (J. Am. Ceram. Soc., 1991, 74, 2547 And heat treated. In this example, m = 1.5 and n = 0.75 were selected in the Si 3 N 4 -Eu 2 O 3 : 9AlN line. The raw materials were mixed at this ratio and milled for 24 hours by ball milling in a non-aqueous solvent, for example nucleic acid. The powder obtained through this was heat-treated for 2 to 8 hours at 1,500 to 1,900 ℃ in a nitrogen atmosphere. The prepared material was pulverized again through a ball mill method, and then subjected to secondary heat treatment in a reducing atmosphere for 2 to 8 hours between 1,000 to 1,500 ° C. again to obtain a predetermined phosphor. The photoluminescence (PL) spectrum of the synthesized phosphor is shown in FIG. 1. (A) of FIG. 1 is an excitation spectrum, (b) is a light emission spectrum.
본 발명에 따른 형광체를 청색 LED에 혼입함으로써 형광체와 LED가 결합되어 새로운 색을 내는 LED를 제조하였다. 이에 대한 LED 제조방법을 간단히 설명하면 다음과 같다. 합성된 시알론 형광체를 적정량(여기서 적정량이라 함은 에폭시수지와 형광체의 질량비를 뜻한다. 본 실험에서는 형광체의 양을 에폭시수지에 대해서 5 내지 80중량%까지 조절하여 실험하였다)을 측정하는 한편, LED용으로 사용되는 에폭시수지와 경화제를 적정량(여기서 적정량이라 함은 에폭시수지와 경화제의 질량비를 뜻한다. 본 실험에서는 경화제의 양을 에폭시수지에 대해서 30 내지 70중량%까지 조절하여 실험하였다)으로 섞어 잘 혼합시켰다. 그 다음, 측정된 형광체를 에폭시수지 혼합물에 주입하여 잘 혼합하고 탈포과정을 거치도록 하였다. 이 혼합물의 적정량을 LED에 주입한 후, 100 내지 200℃의 온도를 유지하는 진공건조기에 넣고 1시간정도 열처리를 하였다.By incorporating the phosphor according to the present invention into a blue LED, the phosphor and the LED were combined to produce a new color LED. The LED manufacturing method for this is briefly described as follows. While measuring the appropriate amount of synthesized sialon phosphor (where appropriate amount refers to the mass ratio of epoxy resin and phosphor. In this experiment, the amount of phosphor was adjusted to 5 to 80% by weight with respect to epoxy resin). Epoxy resin and curing agent used for LEDs (where appropriate amount means mass ratio of epoxy resin and curing agent. In this experiment, the amount of curing agent was adjusted to 30 to 70% by weight with respect to epoxy resin) Mix and mix well. Then, the measured phosphor was injected into the epoxy resin mixture to mix well and undergo a defoaming process. After injecting an appropriate amount of the mixture into the LED, the mixture was put in a vacuum dryer maintaining a temperature of 100 to 200 ℃ heat treatment for about 1 hour.
이를 통해 제조되는 백색 LED의 대표적인 색좌표는 x=0.31, y=0.32 이었다.Typical color coordinates of the white LED manufactured through this were x = 0.31 and y = 0.32.
실시예 2 (Y-Si-Al-O-N 계 시알론 형광체/활성제:유로퓸 이온)Example 2 (Y-Si-Al-O-N-based sialon phosphor / activator: europium ion)
본 발명에 따른 형광체로서 실시예1에 비해 본 예에서는 Ca 대신에 Y를 사용하였다. 원료(raw materials)로 α-Si3N4, SiO2, Y2O3, Eu2O3, Al2O3가 사용되었으며, 고체용액을 형성하는 영역(참고문헌:J. Am.Ceram. Soc., 1991,74,2547)에서 측량하여 열처리되었다. 원료를 혼합하기에 앞서 상기 원료물질을 900℃에서 열처리 한 후, 측량되었으며 적정비율로 혼합되었다. 본 실시 예에서 각 성분의 원자%는 Eu, Y, Si, Al, O, N 이 각각 1.5, 13.7, 14.7, 8.7, 54.0, 7.4%이였다. 이를 통해 나온 분체를 적절한 크기의 펠렛 형태로 만든 후, 환원분위기에서 1,500 내지 1,900℃ 사이에서 2 내지 8시간 동안 열처리를 하였다. 이를 통해 제조된 물질을 다시 볼밀법을 통해 분쇄시킨 후, 700 내지 1,500℃ 사이에서 다시 2 내지 8시간 동안 2차 열처리를 하여 소정의 형광체를 수득하였다. 합성된 형광체의 PL 스펙트럼을 도 2에 나타내었다. 도 2의 (a)는 여기 스펙트럼이고, (b)는 발광스펙트럼이다.As the phosphor according to the present invention, Y was used in place of Ca in this example compared to Example 1. As raw materials, α-Si 3 N 4 , SiO 2 , Y 2 O 3 , Eu 2 O 3 , and Al 2 O 3 were used, and a region for forming a solid solution (refer to J. Am. Ceram. Soc., 1991,74,2547). Prior to mixing the raw materials, the raw materials were heat-treated at 900 ° C., then measured and mixed at an appropriate ratio. In the present embodiment, the atomic% of each component was 1.5, 13.7, 14.7, 8.7, 54.0, and 7.4% of Eu, Y, Si, Al, O, and N, respectively. The powder thus obtained was made into pellets of an appropriate size, and then heat-treated at 1,500 to 1,900 ° C. for 2 to 8 hours in a reducing atmosphere. The prepared material was pulverized again through a ball mill method, and then subjected to a second heat treatment for 2 to 8 hours again between 700 to 1,500 ° C. to obtain a predetermined phosphor. The PL spectrum of the synthesized phosphor is shown in FIG. 2. (A) of FIG. 2 is an excitation spectrum, (b) is a light emission spectrum.
본 발명에 따른 형광체를 근접 청색 LED( peak 파장:405nm)에 혼입함으로써 형광체와 LED가 결합되어 백색을 내는 LED를 제조하였다. 이에 대한 LED 제조방법은 실시예 1에서 본 바와 같다. 구별되는 것은 본 실시예 2의 도 2에 나타난 바와 같이 시알론 형광체의 주 발광 피크는 600㎚로 적색을 보여준다. 백색 LED를 구현하기 위해서 시알론 형광체와 녹색을 발광하는 티오갈레이트(SrGa2S4:Eu ; thiogallate) 형광체를 혼합하여 에폭시와 혼합하였다. 이 때 색좌표는 티오갈레이트와 시알론 형광체의 비율에 따라 조정할 수 있었다.By incorporating the phosphor according to the present invention into a near blue LED (peak wavelength: 405 nm), the LED was produced by combining the phosphor with the LED to give white color. LED manufacturing method for this is as shown in Example 1. What is distinguished is that, as shown in FIG. 2 of Example 2, the main emission peak of the sialon phosphor shows red color at 600 nm. In order to implement a white LED, a sialon phosphor and a thiogallate (SrGa 2 S 4 : Eu; thiogallate) phosphor emitting green color were mixed and mixed with an epoxy. At this time, the color coordinates could be adjusted according to the ratio of thiogallate and sialon phosphor.
실시예 3 (Ca-Si-Al-O-N 시알론 형광체/활성제:유로퓸 이온)Example 3 (Ca-Si-Al-O-N sialon phosphor / activator: europium ion)
본 발명에 따른 형광체와 상용 황색 형광체인 스트론튬바륨실리케이트를 혼합, 근자외선 LED에 혼입함으로써 백색 LED를 제조하였다(스트론튬바륨실리케이트 합성에 관한 참고문헌 : J.Electrochemical Society: SOLID STATE SCIENCE, Vol. 115, No. 11, p 1181-1184 1968). 제조방법은 다음과 같다. 본 발명에 따른 Ca1.47Eu0.03Si9Al3N16적색 형광체, 청색 형광체인 SrOㆍ2Al2O3:Eu 및 2SrOㆍ3Al2O3:Eu와 스트론튬바륨실리케이트를 적정량(여기서 적정량이라 함은 에폭시수지와 형광체의 질량비를 뜻한다. 본 실험에서는 형광체의 양을 에폭시수지에 대해서 5 내지 80중량%까지 조절하여 실험하였다)을 측정하는 한편, LED용으로 사용되는 에폭시수지와 경화제를 적정량(여기서 적정량이라 함은 에폭시수지와 경화제의 질량비를 뜻한다. 본 실험에서는 경화제의 양을 에폭시수지에 대해서 30 내지 70중량%까지 조절하여 실험하였다)으로 섞어 잘 혼합하였다. 그 다음, 혼합된 형광체의 적정량을 에폭시수지 혼합물에 주입하여 잘 혼합하고 탈포과정을 거치도록 하였다. 이 혼합물의 적정량을 LED에 주입한 후, 100 내지 200℃의 온도를 유지하는 진공건조기에 넣고 1시간정도 열처리를 하였다.A white LED was prepared by mixing the phosphor according to the present invention and strontium barium silicate, which is a commercial yellow phosphor, into a near-ultraviolet LED (Reference for the synthesis of barium silicate: No. 11, p 1181-1184 1968). The manufacturing method is as follows. According to the invention Ca 1.47 Eu 0.03 Si 9 Al 3 N 16 red phosphor, a blue phosphor of SrO and 2Al 2 O 3: Eu and 2SrO and 3Al 2 O 3: a suitable amount of Eu and strontium barium silicate (hereinafter referred to as a suitable amount where the epoxy In this experiment, the amount of phosphor was adjusted to 5 to 80% by weight with respect to epoxy resin, and the appropriate amount of epoxy resin and curing agent used for LEDs was measured. This refers to the mass ratio of the epoxy resin and the curing agent In this experiment, the amount of the curing agent was adjusted to 30 to 70% by weight based on the epoxy resin and mixed well). Then, an appropriate amount of the mixed phosphor was injected into the epoxy resin mixture to mix well and undergo a defoaming process. After injecting an appropriate amount of the mixture into the LED, the mixture was put in a vacuum dryer maintaining a temperature of 100 to 200 ℃ heat treatment for about 1 hour.
도 3의 (a)의 본 발명에 의한 시알론 형광체 (Ca1.47Eu0.03Si9Al3N16)의 여기 및 발광스팩트럼을 나타내고 있다. 이 때 얻어지는 색좌표는 x=0.31, y=0.34 이었으며 자연광과 매우 비슷한 모습을 보여주고 있음을 확인할 수 있었다.Excitation and emission spectra of the sialon phosphor (Ca 1.47 Eu 0.03 Si 9 Al 3 N 16 ) according to the present invention of FIG. 3 (a) are shown. The color coordinates obtained at this time were x = 0.31 and y = 0.34, which showed very similar appearance to natural light.
상기한 실시예들을 종합한 결과, 본 발명에 따라 발광다이오드(LED)를 여기원으로 사용하여 시알론 형광체를 발광시킴으로써 백색광을 방출하는 발광 LED 소자를 제작하는 것이 매우 유효함을 입증하였다. 즉, 청색 스펙트럼을 방출하는 Blue LED에 의해 여기되어 오렌지색을 발광하는 시알론 형광체를 도포하여 백색광을 얻을 수 있었으며, 티오갈레이트와 혼합하여 연색성이 우수한 백색 LED를 얻을 수 있었다. 또한 근자외선 스펙트럼(near UV spectrum) 범위에서 방출되는 광원에 의해 여기되어 적색을 발광하는 시알론 형광체와 스트론튬알루미네이트 형광체 및 이를 포함하면서 스트론튬 바륨 실리케이트와의 혼합에 의해 백색광을 방출하는 발광다이오드를 제조할 수 있음을 확인할 수 있었다As a result of the synthesis of the above embodiments, it was proved that according to the present invention, it was very effective to manufacture a light emitting LED device emitting white light by emitting a sialon phosphor by using a light emitting diode (LED) as an excitation source. That is, a white light was obtained by applying a sialon phosphor excited by a blue LED emitting blue spectrum to emit an orange color, and a white LED having excellent color rendering property was obtained by mixing with thiogallate. In addition, a light emitting diode emitting white light by mixing with a strontium aluminate phosphor containing sialon phosphor and strontium aluminate phosphor which is excited by a light source emitted in the near UV spectrum and emits red light is produced. I could confirm that I could
따라서, 본 발명에 의하면 YAG:Eu 형광체를 대체할 양호한 오렌지색 발광 형광체, 적색 발광 형광체 및 이를 이용한 백색광 방출 발광다이오드를 제공하는 효과가 있다.Therefore, according to the present invention, there is an effect of providing a good orange light emitting phosphor, a red light emitting phosphor, and a white light emitting light emitting diode using the same, to replace the YAG: Eu phosphor.
이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100681498B1 (en) * | 2005-03-18 | 2007-02-09 | 가부시키가이샤후지쿠라 | Powdered fluorescent material and method for manufacturing the same, light-emitting device, and illumination apparatus |
| WO2008111878A3 (en) * | 2007-03-09 | 2009-04-02 | Victor Andreevich Vorobiev | Light-converting material and a composition for the production thereof |
| KR101255846B1 (en) * | 2005-03-25 | 2013-04-17 | 라이트스케이프 머티어리얼스, 인코포레이티드 | Metal silicate-silica-based polymorphous phosphors and lighting devices |
| KR20130073583A (en) * | 2011-12-23 | 2013-07-03 | 엘지이노텍 주식회사 | Material changing wavelength and light emitting device package including the same |
| KR101877426B1 (en) * | 2011-11-23 | 2018-07-11 | 엘지이노텍 주식회사 | Oxynitride phosphor, and light-emitting device package comprising the same |
| CN108503352A (en) * | 2018-03-27 | 2018-09-07 | 中国科学院上海硅酸盐研究所 | A kind of garnet-base red fluorescence ceramic material and preparation method thereof |
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2003
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100681498B1 (en) * | 2005-03-18 | 2007-02-09 | 가부시키가이샤후지쿠라 | Powdered fluorescent material and method for manufacturing the same, light-emitting device, and illumination apparatus |
| KR101255846B1 (en) * | 2005-03-25 | 2013-04-17 | 라이트스케이프 머티어리얼스, 인코포레이티드 | Metal silicate-silica-based polymorphous phosphors and lighting devices |
| WO2008111878A3 (en) * | 2007-03-09 | 2009-04-02 | Victor Andreevich Vorobiev | Light-converting material and a composition for the production thereof |
| KR101877426B1 (en) * | 2011-11-23 | 2018-07-11 | 엘지이노텍 주식회사 | Oxynitride phosphor, and light-emitting device package comprising the same |
| KR20130073583A (en) * | 2011-12-23 | 2013-07-03 | 엘지이노텍 주식회사 | Material changing wavelength and light emitting device package including the same |
| CN108503352A (en) * | 2018-03-27 | 2018-09-07 | 中国科学院上海硅酸盐研究所 | A kind of garnet-base red fluorescence ceramic material and preparation method thereof |
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