KR101164960B1 - Boron nitride-based phosphor and method for preparing thereof - Google Patents

Abstract

PURPOSE: A boron nitride-based phosphor is provided to be synthesized at low temperature, to have high reliability, excellent color coordination, color temperature, and color rendering index. CONSTITUTION: A boron nitride-based phosphor is in chemical formula 1: Mx By Nz : Aw. In chemical formula 1, 0ΔxΔ10, 0<yΔ10, 0<zΔ10, 0<wΔ10, and M is one or more kinds selected from family one alkali metals, alkali earth metals, transition metals, and non-transition metals, B is boron, N is nitrogen, and A is one or more selected from rare earth elements and transition metals, but in case M is transition metal, A is not transition metal. In X-ray diffraction pattern by CoKα ray, when putting the relative intensity of the diffraction peak having maximum intensity as 100%, the Bragg angle(2θ) of the X ray diffraction pattern within 26.5-27.5 ° and 31-32 ° has diffraction peak of 10% or more.

Description

Boron nitride-based phosphor and method for preparing the same

The present invention is a boron nitride-based phosphor excited by the compound semiconductor and having a wavelength range of 490 to 780 nm, excellent thermal properties, high reliability and excellent color coordinates, color temperature and color rendering index and a method for producing the same It is about.

Recently, there are several methods of manufacturing gallium nitride (GaN) based light emitting diodes (LEDs), which have been actively promoted worldwide.

a) a method of displaying white by adjusting mixed brightness by simultaneously lighting blue, green, and red LED chips to adjust the brightness of the LEDs; And

b) Method of lighting at the same time by appropriately adjusting the brightness of blue, yellow or orange LED chip.

However, the two multi-chip type methods have problems such as non-uniformity of operating voltage for each chip and color output of each chip due to the ambient temperature.

Currently, a method used by a manufacturer is a method using a phosphor, and a typical method is to manufacture a phosphor by applying a phosphor on a blue or ultra violet (UV) LED chip. This method is simpler and more economical than the method using the combination of the multi-chips. In addition, the method using the phosphor can more simply manufacture a light source of a desired color through three-color variable mixing using the phosphor emitting blue, green, red.

However, since the method of using the phosphor changes the primary light source from the light emitting device to the secondary light source of the phosphor, the light source may have brightness, correlated color temperature (CCT) and The color rendering index (CRI) is different.

Currently, a light source is realized by combination of Ga (In) N-LED emitting blue light at about 460nm and YAG: Ce3 + phosphor emitting yellow light.

However, currently commercially available phosphors for white lamps YAG and related series phosphors do not emit blue light by themselves and have poor red light emission characteristics. In addition, in this case, since the excitation light has a narrow width of blue, it is difficult to develop a lamp having various colors on a white background. In addition, it is a big disadvantage that the change in the white light characteristics according to the wavelength change of the blue light is severe. Moreover, according to the above method, it is also a disadvantage to show a very low luminous efficiency in the UV excitation light.

In addition, although there is an alkaline earth silicate-based phosphor using europium as an activator on a blue LED chip, such a phosphor has a problem of lower reliability than a YAG: Ce ³⁺ phosphor.

Therefore, recently, a method using nitride phosphors has been developed to secure higher reliability than the YAG: Ce ³⁺ phosphor.

For example, conventional nitride-based phosphors include phosphors having chemical formulas of MAlSiN ₃ , M ₂ Si ₅ N ₈ , and MSi ₂ O ₂ N ₂ . However, since the conventional nitride phosphor requires a high temperature / high pressure synthesis process, the process is cumbersome and complicated, and also has the disadvantage of requiring an expensive nitride material.

An object of the present invention is to provide a boron nitride-based phosphor having a wavelength range of 490 to 780 nm and excellent thermal properties, and a method of manufacturing the same.

Another object of the present invention is to provide a light emitting device comprising the boron nitride-based phosphor.

The present invention provides a boron nitride-based phosphor represented by the following formula (1).

[Formula 1]

M _x B _y N _z : A _w

In the above formula, 0≤x≤10, 0 <y≤10, 0 <z≤10, 0 <w≤10, and M is in the group consisting of Group 1 alkali metals, alkaline earth metals, transition metals and non-transition metals At least one selected, B is a boron atom, N is a nitrogen atom, A is at least one selected from the group consisting of rare earth elements and transition metals, provided that A is not a transition metal when M is used )

In another aspect, the present invention provides a method for producing a boron nitride-based phosphor represented by the formula (1) comprising the following steps:

a) at least one metal oxide, metal carbonate or metal nitride selected from the group consisting of i) alkali metals, alkaline earth metals, transition metals and non-transition metals, ii) BN, and iii) rare earth elements or transition metal elements At least one compound selected from the group consisting of metal oxides, metal halides or metal nitrides is wet mixed in a solvent or dry mixed without a solvent, and the mixture is dried at a temperature of 50 ° C. to 100 ° C. for 10 minutes to 48 hours. step;

b) heat-treating the mixture obtained in step a) in an atmosphere of 1200 to 2200 ° C. for 1 to 48 hours;

c) pulverizing and classifying the phosphor obtained by the heat treatment in step b) to obtain a phosphor powder having a constant size; And

d) removing the unreacted material by washing the phosphor obtained in step c).

In step a), it may further comprise the step of adding at least one flux selected from the group consisting of NH ₄ Cl, NH ₄ F, and BaF ₂ to the mixture of i) to iii).

In another aspect, the present invention provides a light emitting device comprising the boron nitride-based phosphor of the above formula (1).

Hereinafter, the present invention will be described in detail.

The present invention relates to a boron nitride-based phosphor that can be used as a light source and a light emitting device using the same.

According to one embodiment of the present invention, a boron nitride-based phosphor represented by the following formula (1) is provided.

[Formula 1]

M _x B _y N _z : A _w

In the above formula, 0≤x≤10, 0 <y≤10, 0 <z≤10, 0 <w≤10, and M is in the group consisting of Group 1 alkali metals, alkaline earth metals, transition metals and non-transition metals At least one selected, B is a boron atom, N is a nitrogen atom, A is at least one selected from the group consisting of rare earth elements and transition metals, provided that A is not a transition metal when M is used )

The present invention provides a phosphor comprising essentially boron and nitrogen atoms, the phosphor exhibiting a specific diffraction pattern is a new phosphor different from the nitride phosphor developed previously. Such a phosphor of the present invention exhibits stability of the chemical composition and has excellent thermal properties and can also improve luminescence properties.

In particular, the boron nitride phosphor of the present invention has a Bragg angle of the X-ray diffraction pattern when the relative intensity of the diffraction peak having the greatest intensity is 100% in the powder X-ray diffraction pattern by CoKα rays. 2θ) is characterized by showing a diffraction peak of 10% or more relative strength within the range of 26.5 ° to 27.5 ° and 31 ° to 32 °.

In addition, the boron nitride phosphor of the present invention has a Bragg angle (2θ) of the X-ray diffraction pattern when the relative intensity of the diffraction peak having the greatest intensity is 100% in the powder X-ray diffraction pattern by CoKα rays. It is preferable to include as a main product the phase which shows the diffraction peak of 45% or more of relative intensity within the range of 26 degrees-27 degrees, 29 degrees-30 degrees, and 31 degrees-32 degrees.

The novel boron nitride-based phosphor according to the present invention may have a chemically stable composition by having a main product in the crystal structure defined by the X-ray diffraction pattern. The boron nitride-based phosphor may have a high emission intensity because the peak wavelength of the emission center exhibits a range of 490 nm to 780 nm. Therefore, the present invention can exhibit high excitation characteristics and light emission characteristics in a wide range of wavelengths.

In the present invention, particularly in the case of a light emitting device using a light emitting diode, when the boron nitride phosphor of the present invention is included in a mold material, the light emitting device may be excited by a compound semiconductor and have a light emission central wavelength of 490 nm to 780 nm.

Further, in the above formula (1), it is more preferable that 0≤x≤5, 0 <y≤10, 0.1 <z≤10, and 0 <w≤2. In particular, in the composition of Formula 1, the content of element M may be 10 mol% to 30 mol% based on the total phosphor composition.

In Chemical Formula 1, when the range of x, y, z, w is outside the range of the present invention, the luminescence may be reduced and the center wavelength may be severely shifted if the composition is not satisfied. In particular, the phosphors do not emit sufficient light because the extraction of the main peaks in the X-ray diffraction pattern is outside the range of the desired Bragg angle.

In addition, in the definition of Formula 1, M and A are not simultaneously transition metals, so in this case M ≠ A, whereby A is not a transition metal when M is a transition metal.

In addition, in the case of the boron nitride-based phosphor of the present invention, it is possible to induce a change in the emission center wavelength in accordance with the content of the heat treatment reducing gas, M and A at the time of phosphor production.

For example, the reducing gas may use nitrogen gas or a mixed gas of hydrogen gas and nitrogen gas. In the case where the mixed gas is used, as the volume of hydrogen increases, the emission center wavelength can be shifted toward the longer wavelength of the 660 nm band. In addition, when only nitrogen gas is used as the reducing gas, the center wavelength can be shifted toward the shorter wavelength than the wavelength above the 640 nm band.

In addition, in the content of A used as an activator, when the content of A increases, it is moved toward the shorter wavelength, and when the content of A decreases, it can be moved toward the longer wavelength.

In addition, the wavelength can be changed according to the ratio of B and M. As the B content increases and the M content decreases, the wavelength shifts to a longer wavelength. In addition, the content of B decreases, and as the content of M increases, it moves to shorter wavelengths.

The boron nitride-based phosphor represented by the formula (1) of the present invention may have an average particle size of 20㎛ or less, more preferably 5㎛ to 10㎛.

In Formula 1, M may be one selected from the group consisting of alkali metals including Li, Na, K, and the like, alkaline earth metals including Ca, Ba, and Sr, transition metals, and non-transition metals. For example, M may be any one or more selected from the group consisting of Li, Be, Na, K, Mg, Ca, Zn, Ge, Sr, Cd, Sn, Cs, Ba, Hg, Pb, and Ra, and Preferably Si, Ca, Mg or Sr.

Also A is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , Yb and Lu may be any one or more selected from the group consisting of, more preferably Eu or Mn.

On the other hand, according to another embodiment of the present invention, a) i) at least one metal oxide, metal carbonate or metal nitride selected from the group consisting of alkali metals, alkaline earth metals, transition metals and non-transition metals, ii) BN, and iii) at least one compound selected from the group consisting of metal oxides, metal halides or metal nitrides of rare earth elements or transition metal elements in a solvent or dry mixed with a solvent, and the mixture is mixed for 10 minutes to 48 hours. Drying at a temperature of between 50 ° C. and 100 ° C .; b) heat-treating the mixture obtained in step a) in an atmosphere of 1200 to 2200 ° C. for 1 to 48 hours; c) pulverizing and classifying the phosphor obtained by the heat treatment in step b) to obtain a phosphor powder having a constant size; And d) washing the phosphor obtained in step c) to remove the unreacted material.

The novel method for producing boron nitride-based phosphors according to the present invention may use a solid phase method, but is not necessarily limited thereto.

Specifically, in step a), i) to iii) after weighing a certain amount of the components, they are wet mixed under a solvent or dry mixed without a solvent, the step of drying the mixture is carried out. In addition, the present invention may further comprise the step of adding at least one flux selected from the group consisting of NH ₄ Cl, NH ₄ F, and BaF ₂ to the mixture of i) to iii) as necessary in step a). Can be.

At this time, the content ratio of the i) to iii) components, and iv) components can be used by appropriately weighing in a range satisfying the range of x, y, z, w in order to have a composition formula of the above formula (1).

In addition, i) component is used to form M in the composition of Formula 1, and ii) component is used to form boron and nitrogen atoms. In addition, the component iii) is used as an activator, and an oxide, halide or nitride of a rare earth element or transition metal is used as described above. At this time, examples of the component i) include Ca ₃ N ₂ , Si ₃ N _4, and the like.

In addition, when the wet mixing is carried out, the solvent may be alcohol, acetone or distilled water.

The drying step is not particularly limited to the drying time and temperature conditions, but preferably proceeds in the above-described conditions.

In addition, the heat treatment temperature of step b) is preferably more than the temperature sufficient to complete the reaction. Therefore, after drying the mixture obtained in step a) is preferably heat treated in an atmosphere of 1200 to 2200 ℃, more preferably 1600 to 1800 ℃. That is, if the temperature is less than 1200 ℃ the crystal of the phosphor according to the present invention is not completely produced, the luminous efficiency is reduced, and if it exceeds 2200 ℃ it is difficult to produce a low-luminance or solid-state phosphor powder due to overreaction Problem occurs. In addition, the heat treatment may be performed under a gas of a reducing atmosphere. Although it is preferable to use nitrogen gas or the gas which mixed nitrogen and hydrogen, the said gas is not specifically limited to this. For example, it is preferable to use nitrogen gas mixed with 2 to 25% by volume of hydrogen or nitrogen gas mixed with 5 to 40% by volume of ammonia. However, in some cases, only nitrogen gas may be used.

In particular, in the white light emitting diode according to the present invention, the phosphor used may vary in wavelength depending on the ratio of hydrogen gas during the heat treatment in Chemical Formula 1.

The phosphor obtained in step b) is aggregated due to the high heat treatment temperature, so that the pulverization and classification process is necessary to obtain a powder having a desired brightness and size. Therefore, in the present invention, by performing step c), it is possible to provide a phosphor having improved light emission characteristics. The said pulverization and classification process can be progressed according to a conventional method, The method is not specifically limited. For example, the average particle size of the phosphor after heat treatment may be pulverized to 20 μm or less, and classification of the phosphor may be performed using powder of 25 to 32 μm.

In addition, the phosphor obtained by heat treatment in the reducing atmosphere may include a trace amount of unreacted material as impurities. If such impurities are not removed, there is a problem that the moisture resistance tends to be inferior when manufacturing the light emitting device using the phosphor.

Therefore, in the present invention, in order to solve this problem, the phosphor obtained in step c) is washed by step d) to remove unreacted substances.

In the step of removing the unreacted substance, it is preferable to use at least one polymer solvent in which unreacted substances such as alcohol, acetone or polymer solvent are dissolved. The washing method may include a method in which the phosphor is added to the above-mentioned solvent and mixed and then dried, but is not particularly limited thereto.

On the other hand, according to another embodiment of the present invention, there is provided a light emitting device comprising the above-described boron nitride-based phosphor of formula (1).

The light emitting device of the present invention includes a light source for emitting light, a substrate supporting the light source, a molding member molded around the light source, and the molding member includes a boron of Chemical Formula 1, which is a single structure or multiple structures. At least one nitride-based phosphor is characterized in that it comprises.

The emission center wavelength of the boron nitride-based phosphor excited by the light emitting device may have a wavelength range of 490 nm to 780 nm.

In addition, the light emitting device includes a light emitting diode, a laser diode, a surface emitting laser diode, an inorganic electroluminescent device, or an organic electroluminescent device.

When the light emitting device is a light emitting diode, the light emitting diode chip may include a blue light emitting diode chip. In addition, the light emitting diode chip and the phosphor of the light emitting diode may be molded by a light transmitting resin.

The light transmitting resin may include a light transmitting resin as a molding member. The molding member may be formed in a single structure or multiple structures, and may function as an exterior material. The light transmitting resin is preferably a light transmitting epoxy resin, a light transmitting silicone resin or a mixture thereof. In addition, the light transmitting resin may be used by mixing with polyimide resin, urea resin, acrylic resin. In this case, the phosphor may be mixed with a silicone resin, a polyimide resin, a urea resin, and an acrylic resin in addition to an epoxy resin to form a white light emitting diode by molding the periphery of the light emitting diode chip.

In addition, the phosphor may be mixed with other phosphors in addition to the phosphor according to the embodiment of the present invention. Preferably, the light emitting device may include any one or more phosphor mixtures selected from the group consisting of silicates, phosphates, oxides, oxynitrides, and nitride-based phosphors, together with boron nitride-based phosphors of Chemical Formula 1.

In addition, the present invention provides a coating phosphor composition for a light emitting device comprising the boron nitride-based phosphor of Formula 1 and a light transmitting resin. The phosphor of Chemical Formula 1 and the light transmitting resin may be mixed in all weight ratios, but may be preferably mixed in a weight ratio of 1: 10 to 1: 20.

1 illustrates a structure of a white light emitting diode according to an exemplary embodiment of the present invention.

Referring to FIG. 1, the white light emitting diode of the present invention serves as a reflector for reflecting light emitted from the InGaN-based light emitting diode chip 110 and the light emitting diode chip 110 above the white light emitting diode. 120), a bonding wire 140 for electrically connecting the light emitting diode chip 110 and the lead frames 130 of the positive electrode and the negative electrode, and a colorless or colored light transmission molding the whole around the light emitting diode chip 110. It includes a packaging material 150 made of a resin, the fluorescent material 160 is wholly or partially dispersed in the packaging material.

In this case, the phosphor 160 may include at least one boron nitride-based phosphor of Formula 1, and at least one other phosphor may be mixed.

In the present invention, instead of the light emitting diode chip 110 generating light having a center wavelength of 460 nm, a light emitting device having a light emitting peak in the same wavelength region as a laser diode, a surface emitting laser diode, an inorganic electroluminescent device, You may use an organic electroluminescent element etc. as a light source.

Therefore, the light emitting device may be a laser diode including a light emitting diode, a surface emitting laser diode, an inorganic electroluminescent device, or an organic electroluminescent device.

In the present invention, in place of the garnet-based phosphors, alkaline earth silicate-based phosphors, and the like, which are conventionally used, there is an effect of providing boron nitride-based phosphors having more reliable and high-performance white light emission characteristics. In addition, the present invention can be synthesized at a low temperature instead of the high temperature, high pressure synthesis process in the synthesis of phosphors of the conventional nitride system has an economic effect of reducing the manufacturing cost. Therefore, the phosphor of the present invention is effective for use as an illumination light source for color LCD backlights, LED lamps, monitors, notebooks of mobile phones.

1 is a view showing the structure of a white light emitting diode according to an embodiment of the present invention.
Figure 2 shows the emission spectrum of the white light emitting diode of the phosphor according to Example 1 of the present invention.
3 shows an X-ray diffraction pattern of the phosphor of Example 1 of the present invention.
4 shows the emission spectrum of the white light emitting diode of the phosphor according to Example 2 of the present invention.
5 shows an X-ray diffraction pattern of the phosphor of Example 2 of the present invention.
Figure 6 shows the emission spectrum of the white light emitting diode of the phosphor according to Example 3 of the present invention.
7 shows the X-ray diffraction pattern of the phosphor of Example 3 of the present invention.
8 shows the emission spectrum of the white light emitting diode of the phosphor according to Example 4 of the present invention.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through a specific embodiment of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

Example 1

1.2056 g of BN, 0.3933 g of Si ₃ N _{4, and} 0.4928 g of Eu ₂ O _{3 were} added to acetone and wet mixed for 10 hours using a ball mill. The mixture was placed in a 100 ° C. drier and dried for 1 hour to completely volatilize the solvent. The mixed materials were placed in Graphite and BN crucibles and heat-treated at 1800 ° C. for 20 hours. At this time, 100% nitrogen, 2%, 5%, and 15% of the nitrogen mixed gas mixed with hydrogen was flowed while flowing 1000 cc / min. When the heat treatment was completed, the phosphor was pulverized. Since the pulverized phosphor contained unreacted material, it was placed in distilled water and sonicated for 30 minutes and then dried. When the drying is completed, a boron nitride-based phosphor was prepared by classifying a phosphor having a constant size using powder.

The phosphor prepared by the above manufacturing process is M _x B _y N _z : A _w (wherein x is 0.15, y is 0.85, z is 0.9 to 2.0, w is 0.05, and M = Si, B is a boron atom). N represents a nitrogen atom and A represents an Eu atom (formula 1-1 below).

Then, a white light emitting diode as shown in FIG. 1 was manufactured using the boron nitride phosphor of Formula 1-1 and InGaN light emitting diode chip 110 having a center wavelength of about 460 nm.

Specifically, the boron nitride-based fluorescent material 160 of Formula 1-1 prepared by the blue light (460 nm) generated from the light emitting diode chip 110 in the packaging material 150 made of a light transmitting epoxy resin is The mixture was molded to surround the light emitting diode chip 110. In this case, the boron nitride phosphor 160 of Formula 1-1 is excited by blue light (460 nm) generated from the light emitting diode chip 110 to emit light having a wavelength of about 650 nm (light emission center wavelength).

In addition, in Example 1 of the phosphor according to the present invention, the emission spectrum of the phosphor for providing a white light emitting diode is shown in FIG. 2.

As shown in Figure 2, in the case of the present invention it can be seen that the wavelength can be changed in various ways depending on the ratio of hydrogen gas.

In the white light emitting diode according to the present invention, the phosphor used varies in wavelength depending on the ratio of hydrogen gas in the formula (1-1). As the hydrogen volume increases in the phosphor, it was confirmed that the central wavelength can be moved to a long wavelength close to 660 nm. On the contrary, when the volume of hydrogen in the phosphor decreases, it tends to move to a short wavelength, and preferably, when heat is added without nitrogen, heat is approached to 640 nm. Therefore, within the above range, the phosphor of the present invention exhibited a central wavelength of 640 nm to 660 nm.

3 illustrates an X-ray diffraction pattern of the phosphor of Chemical Formula 1-1 of Example 1. FIG. As shown in FIG. 3, the phosphor of the present invention has a Bragg angle of the X-ray diffraction pattern when the relative intensity of the diffraction peak having the greatest intensity is 100% in the powder X-ray diffraction pattern by CoKα rays. , 2θ) included a phase showing a diffraction peak of 10% or more in a relative intensity within a range of 26.5 ° to 27.5 ° and 31 ° to 32 ° as a main product.

Example 2

1.2592 g of BN, 0.4108 g of Si ₃ N _4, 0.4118 g of Eu ₂ O ₃ , and 0.0415 g of MnO were added to acetone and wet mixed for 10 hours using a ball mill. The mixture was placed in a 100 ° C. drier and dried for 1 hour to completely volatilize the solvent. The mixed materials were placed in an alumina crucible and heat-treated at 1600 ° C. for 20 hours. At this time, 100% nitrogen was heat-treated while flowing 1000 cc / min. When the heat treatment was completed, the phosphor was pulverized. Since the pulverized phosphor contained unreacted material, it was placed in distilled water and sonicated for 30 minutes and then dried. When the drying is completed, a boron nitride-based phosphor was prepared by classifying a phosphor having a constant size using powder.

The phosphor prepared by the above manufacturing process is M _x B _y N _z : A _w (wherein x is 0.15, y is 0.85, z is 0.9 to 2.0, w is 0.05, and M = Si, B is a boron atom). , N is a nitrogen atom, and A is Eu and Mn).

Then, a white light emitting diode was manufactured as shown in FIG. 1 using the boron nitride phosphor of Formula 1-2 and an InGaN light emitting diode chip 110 having a center wavelength of about 460 nm.

Specifically, the boron nitride-based phosphor 160 of Chemical Formula 1-2 prepared by the blue light (460 nm) generated from the light emitting diode chip 110 in the packaging material 150 formed of the light transmitting epoxy resin. The mixture was molded to surround the light emitting diode chip 110. At this time, the boron nitride-based fluorescent material 160 of Formula 1-2 prepared above is excited by blue light (460 nm) generated from the light emitting diode chip 110 to emit light having a range of 558 nm (light emission center wavelength).

The emission spectrum of the phosphor for the white light emitting diode in Example 2 of the phosphor according to the present invention is shown in FIG. 4.

Referring to FIG. 4, in the white light emitting diode according to the present invention, phosphors having a completely different wavelength from those of Example 1 may be made by adding Mn in Example 2. In Example 2, the phosphor of the present invention exhibited a light emission central wavelength of 550 nm to 570 nm.

5 illustrates an X-ray diffraction pattern of the phosphor of Chemical Formula 1-2 of Example 2. FIG.

Example 3

0.2930 g of Ca ₃ N _2, 0.6537 g of BN, 0.7251 g of Si ₃ N _{4, and} 0.4130 g of Eu ₂ O _{3 were} added to acetone and wet mixed for 10 hours using a ball mill. The mixture was placed in a 100 ° C. drier and dried for 1 hour to completely volatilize the solvent. The mixed materials were placed in an alumina crucible and heat-treated at 1600 ° C. for 20 hours. At this time, 100% nitrogen was heat-treated while flowing 1000 cc / min. When the heat treatment was completed, the phosphor was pulverized. Since the pulverized phosphor contained unreacted material, it was placed in distilled water and sonicated for 30 minutes and then dried. When the drying is completed, a boron nitride-based phosphor was prepared by classifying a phosphor having a constant size using powder.

The phosphor prepared by the above manufacturing process is M _x B _y N _z : A _w (wherein M is Ca, Si (Ca = 0.12, Si = 0.5), y = 0.33, z = 1-2, w = 0.05, B is a boron atom, N is a nitrogen atom, and A is an Eu atom).

Then, a white light emitting diode was manufactured as shown in FIG. 1 using the boron nitride phosphor of Formula 1-3 and an InGaN light emitting diode chip 110 having a center wavelength of about 460 nm.

Specifically, the boron of Chemical Formula 1-3 prepared above having a center wavelength of 590 nm excited by the blue light (460 nm) generated by the light emitting diode chip 110 in the packaging material 150 formed of the light transmitting epoxy resin. The nitride yellow phosphor 160 was mixed and molded to surround the light emitting diode chip 110. At this time, the boron nitride phosphor 160 of Formula 1-3 is excited by blue light (460nm) generated from the light emitting diode chip 110 to emit light having a center wavelength of 590nm (light emitting center). wavelength).

In Example 3 of the phosphor according to the present invention, the emission spectrum of the phosphor for the white light emitting diode is shown in FIG. 6.

Referring to FIG. 6, in the white light emitting diode according to the present invention, it can be seen that the phosphor used may vary in wavelength depending on the ratio of B and Si in Formula 1-3.

In Example 3, as the amount of B (b value) increases and the amount of Si (c value) decreases, it tends to shift to a longer wavelength. On the contrary, in Example 3 of the phosphor, as the amount of B (b value) decreases and the amount of Si (c) increases, it tends to shift to shorter wavelengths. Within the above range, the phosphor of the present invention exhibited a light emission central wavelength of 570 nm to 610 nm.

7 illustrates X-ray diffraction patterns of the phosphor of Chemical Formula 1-3 of Example 3. FIG. As shown in FIG. 7, the phosphor of the present invention has a Bragg angle of the X-ray diffraction pattern when the relative intensity of the diffraction peak having the greatest intensity is 100% in the powder X-ray diffraction pattern by CoKα rays. 2θ) included diffraction peaks with a relative intensity of 45% or more in the range of 26 ° to 27 °, 29 ° to 30 °, and 31 ° to 32 ° as main production phases.

Example 4

0.7854 g of BaCO _3, 0.2771 g of BN, 0.3881 g of ZnO 0.6756 g Si ₃ N _{4, and} 0.2918 g of Eu ₂ O _{3 were} added to acetone and wet mixed for 10 hours using a ball mill. The mixture was placed in a 100 ° C. drier and dried for 1 hour to completely volatilize the solvent. The mixed material was placed in an alumina crucible and heat treated at 1650 ° C. for 10 hours. At this time, 95% nitrogen and 5% hydrogen were heat-treated while flowing 1000 cc / min. When the heat treatment was completed, the phosphor was pulverized. Since the pulverized phosphor contained unreacted material, it was placed in distilled water and sonicated for 30 minutes and then dried. When the drying is completed, a boron nitride-based phosphor was prepared by classifying a phosphor having a constant size using powder.

The phosphor prepared by the above manufacturing process is M _x B _y N _z : A _w (wherein M is Ba, Zn, Si (Ba = 0.12, Zn = 0.25, Si = 0.25), y = 0.33, z = 1-2, w = 0.05, B is a boron atom, N is a nitrogen atom, and A is an Eu atom (Formula 1-4).

Then, a white light emitting diode was manufactured as shown in FIG. 1 using the boron nitride phosphor of Formula 1-4 and an InGaN light emitting diode chip 110 having a center wavelength of about 460 nm.

Specifically, the boron of Chemical Formula 1-4 manufactured in the above having a center wavelength of 529 nm excited by the blue light (460 nm) generated by the light emitting diode chip 110 in the packaging material 150 formed of the light transmitting epoxy resin. The nitride greenish green phosphor 160 was mixed and molded to surround the light emitting diode chip 110. In this case, the boron nitride phosphor 160 of Formula 1-4 is excited by blue light (460 nm) generated from the light emitting diode chip 110 to emit light having a center wavelength of 529 nm (light emitting center). wavelength).

In Example 4 of the phosphor according to the present invention, the emission spectrum of the phosphor for the white light emitting diode is shown in FIG. 8.

110: light emitting diode chip
120: reflection cup
130: lead frame
140: bonding wire
150: exterior material
160: phosphor

Claims (15)

When the relative intensity of the largest intensity diffraction peak in the powder X-ray diffraction pattern by CoKα ray is 100%, the Bragg angle (2θ) of the X-ray diffraction pattern is 26.5 ° to 27.5 ° and 31 ° to Boron nitride-based phosphor represented by the following formula (1) showing a diffraction peak of 10% or more relative intensity within a range of 32 °.
[Formula 1]
M _x B _y N _z : A _w
In the above formula, 0≤x≤10, 0 <y≤10, 0 <z≤10, 0 <w≤10, and M is in the group consisting of Group 1 alkali metals, alkaline earth metals, transition metals and non-transition metals At least one selected, B is a boron atom, N is a nitrogen atom, A is at least one selected from the group consisting of rare earth elements and transition metals, provided that A is not a transition metal when M is used ) delete The method of claim 1,
When the relative intensity of the largest intensity diffraction peak in the powder X-ray diffraction pattern by CoKα ray is 100%, the Bragg angle (2θ) of the powder X-ray diffraction pattern is 26 ° to 27 ° and 29 ° Boron nitride-based phosphors exhibiting diffraction peaks of 45% or more in relative intensity within a range of 30 ° and 31 ° to 32 °. The boron nitride phosphor of claim 1, wherein in Formula 1, 0 ≦ x ≦ 5, 0 <y ≦ 10, 0.1 <z ≦ 10, and 0 <w ≦ 2. The boron nitride-based phosphor according to claim 1, wherein the emission center wavelength has a wavelength band of 490 to 780 nm. According to claim 1, wherein in Formula 1,
M is at least one selected from the group consisting of Li, Be, Na, K, Mg, Ca, Zn, Ge, Sr, Cd, Sn, Cs, Ba, Hg, Pb and Ra,
A is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Boron nitride-based phosphor, any one or more selected from the group consisting of Yb and Lu Method for preparing a boron nitride-based phosphor represented by the formula (1) of claim 1 comprising the following steps:
a) at least one metal oxide, metal carbonate or metal nitride selected from the group consisting of i) alkali metals, alkaline earth metals, transition metals and non-transition metals, ii) BN, and iii) rare earth elements or transition metal elements At least one compound selected from the group consisting of metal oxides, metal halides or metal nitrides is wet mixed in a solvent or dry mixed without a solvent, and the mixture is dried at a temperature of 50 ° C. to 100 ° C. for 10 minutes to 48 hours. step;
b) heat-treating the mixture obtained in step a) in an atmosphere of 1200 to 2200 ° C. for 1 to 48 hours;
c) pulverizing and classifying the phosphor obtained by the heat treatment in step b) to obtain a phosphor powder having a constant size; And
d) removing the unreacted material by washing the phosphor obtained in step c). The method of claim 7, wherein in step a),
A method of producing a boron nitride-based phosphor further comprising the step of adding at least one flux selected from the group consisting of NH ₄ Cl, and BaF ₂ to the mixture of i) to iii). 8. The method of claim 7, wherein the solvent is alcohol, acetone or distilled water. A light emitting device comprising the boron nitride-based phosphor of any one of claims 1, 3 to 6. The light emitting device of claim 10, wherein the light emitting device is a light emitting diode, a laser diode, a surface emitting laser diode, an inorganic electroluminescent device, or an organic electroluminescent device. The light emitting device according to claim 10, wherein the emission center wavelength of the boron nitride-based fluorescent material excited by the light emitting device has a wavelength band of 490 to 780 nm. The method of claim 10,
Boron nitride-based phosphors of Formula 1, and
A light emitting device comprising any one or more phosphor mixtures selected from the group consisting of silicates, phosphates, oxides, oxynitrides and nitride-based phosphors. The light emitting device of claim 10, wherein the light emitting diode chip comprises a blue light emitting diode chip when the light emitting device is a light emitting diode. The light emitting device of claim 14, wherein the light emitting diode chip and the phosphor of the light emitting diode are molded by a light transmitting resin.

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