TWI431098B - Method for prceise control of element composition ration of fired phosphor, phosphor produced by the same and light-emission device containing the phosphor - Google Patents

Description

Method for accurately controlling the proportion of structural components of fired phosphors, phosphors obtained therefrom, and light-emitting devices containing the same

The present invention relates to a method for accurately controlling the proportion of a fired structural component of a fired body, a phosphor produced by the method, and particularly a device suitable for a display or a light-emitting diode. A red phosphor that emits red wavelength light after being excited by the device. The invention also provides a light emitting device comprising the red phosphor.

Under the demands of energy conservation and environmental protection, the development of high-efficiency, energy-saving and environmentally-friendly lighting sources has become an important research topic, especially in light-emitting diodes (LEDs) due to their small size and heat. It has the advantages of low quantity, low power consumption and long life, and it has the disadvantages of incandescent bulbs, high power consumption, fragility and mercury pollution of fluorescent lamps, which has become an important technology to replace traditional lighting fixtures. At present, most of the white light-emitting devices used for illumination are mainly composed of blue light as an excitation light source and a yellow phosphor. However, the red light band emitted by the white light emitting device is insufficient, so that the color rendering and color saturation of the white light are obviously insufficient, and the yellow phosphor of the prior art has poor luminous efficiency, so that the white light brightness is not good. In order to solve the above problems, in recent years, it has been actively developed to mix a yellow phosphor into a phosphor that emits red light to enhance the color rendering and color saturation of the white light, and to supplement the yellow phosphor light through the red phosphor. The disadvantage of poor efficiency.

Currently known red phosphors such as Sr ₂ Si ₅ N ₈ :Eu, CaAlSiN ₃ :Eu or sialon phosphors (generally M _z Si _12-(m+n) Al _m+n O _n N _16-n ). However, the phosphor of Sr ₂ Si ₅ N ₈ :Eu has disadvantages such as poor heat resistance and long-term use of luminance and color rendering properties; although the Sialon phosphor has no durability problem, its luminosity is obvious. Insufficient, not popular in commercial use; while the CaAlSiN ₃ :Eu phosphor has better durability and better brightness than the sialon phosphor, the industry still expects higher The phosphor of the luminance, and can make the illuminating device have higher luminous efficiency.

For the above-mentioned CaAlSiN ₃ :Eu series red phosphor, such as Ca _m Al _a Si _b N _n :Eu _z , wherein (m+z): a:b:n=1:1:1:3; or Ca _b Si _c Al _d N _x :Eu _a , wherein a+b=1, 0.5≦c≦4, 0.5≦d≦8, all of which can be produced by the preparation process outlined below. First, the tantalum nitride, aluminum nitride, calcium carbonate or calcium nitride and cerium oxide are mixed in a firing vessel according to a predetermined molar ratio, at a high temperature of 1700 ° C and a high pressure of more than 10 atm under nitrogen. It is produced by firing in the environment. The disadvantages of this method are mainly high pressure operation (greater than 10 atmospheres), and are more dangerous, and the cost of energy and equipment is also high. Moreover, the narrow range of chromaticity values of the light emitted by the red phosphor produced by the method has little effect on improving the color rendering and color saturation of the white light, and the brightness is not greatly improved. Still unable to meet the needs of the industry.

It can be seen from the above that there is still a need to develop a red phosphor having higher luminance and high luminous efficiency than the red phosphor of the same system in the prior art, and can enhance the color rendering and color saturation of the white light in subsequent applications. .

Accordingly, a first object of the present invention is to provide a method for accurately controlling the proportion of a structural component of a fired phosphor which can produce a phosphor having a high luminance.

Thus, the method for accurately controlling the proportion of the structure component of the fired phosphor of the present invention comprises the steps of: providing a firing vessel comprising a body having a chamber and a closure for closing the chamber; The light source starting material is placed in the chamber of the main body; a sealant is applied to at least one of the main body and the sealing member; and the firing container is fired in a non-oxidizing gas environment After that, a phosphor is obtained.

A second object of the present invention is to provide a phosphor obtained by the above production method.

In particular, the inventors of the present invention actively researched and developed different red phosphors by the above-mentioned preparation method, which contributes to improving the color rendering and color saturation of white light emitted by the white light emitting device, and can satisfy the industry's high The third object of the present invention is to provide a red phosphor having high luminance.

Thus, the red phosphor has the formula (I): Ca _a Sr _b Al _c Si _d O _e N _f : Eu _g ... (I)

Where 0 ≦ a < 1, 0 < b < 1, c = 1, 0.8 ≦ d ≦ 1.2, 0 ≦ e ≦ 0.5, 2.5 ≦ f ≦ 3.1, 0.002 ≦ g ≦ 0.020, with the condition that a and b cannot simultaneously When it is 0, and the phosphor is excited by light with a wavelength of 455 nm, the CIE1931 color coordinate (x, y) of the emitted light satisfies the following relationship:

x=[(-0.1059b ³ +0.068b ² -0.06b)+(2152.8g ³ -309.2g ² +8.2943g)+0.6324]±0.01;

y=[(0.1295b ³ -0.0968b ² +0.0702b)+(-3299.2g ³ +311.08g ² -7.9266g)+0.3621]±0.01.

A fourth object of the present invention is to provide a light-emitting device having better color rendering, color saturation and high luminous efficiency, comprising a light-emitting unit comprising a light-emitting element and a red phosphor as described above.

The effect of the present invention is that the use of the adhesive in the present invention enables the elements to be effectively combined in a predetermined ratio to form an optimized phosphor composition, so that the chemical formula and the composition of the obtained phosphor are obtained. The difference is not large, not only can reduce the cost, but also a phosphor having high luminance characteristics can be obtained, so that the chromaticity and high luminance characteristics of the light emitted by the phosphor of the present invention are the same system of the prior art. The phosphor can not be achieved, and the phosphor helps to improve the color rendering and color saturation of the white light emitted by the white light emitting device, and can provide different choices in the industry, so that the effect of the present invention is achieved.

The method for accurately controlling the proportion of the fired structural component of the present invention comprises the steps of: providing a firing container comprising a body having a chamber and a closure for closing the chamber; and a phosphor The starting material is placed in the chamber of the main body; at least one of the main body and the sealing member is applied to the main body and the sealing member; and after the firing container is fired in a non-oxidizing gas atmosphere, Obtain a phosphor.

Preferably, the binder forms a dense structure during the firing process.

Preferably, the binder binds the body to the closure without a gap during the firing process and causes the firing vessel to be in an airtight state.

Preferably, the material of the firing container is selected from SiAlON, aluminum nitride (such as AlN), boron nitride (such as BN) or a combination thereof. More preferably, a firing container made of boron nitride is preferred.

When the phosphor of the present invention is prepared, the phosphor starting material contains at least one element source, which is a nitride, an oxide or a metal constituting the element of the phosphor. The above-mentioned "oxide" is not limited to a compound which is only oxidized, such as a carbonate, an oxalate or the like which decomposes into the above element and oxygen during the firing treatment, and the carbonate or oxalate also belongs to the compound. The scope of "oxide"; the case of "nitride" is also as described above. Preferably, the phosphor starting material comprises at least one of an aluminum source, a germanium source, a germanium source, and a calcium source or a germanium source. Preferably, the aluminum source, the germanium source, the germanium source, the calcium source and the germanium source are aluminum nitride, germanium nitride, germanium oxide, calcium nitride and germanium nitride, respectively. In a specific example of the present invention, the nitride of aluminum is aluminum nitride (chemically AlN), the nitride of niobium is tantalum nitride (silicon nitride, chemical formula Si ₃ N ₄ ), and the oxide of niobium is Cerium oxide (Euopium oxide, chemical formula Eu ₂ O ₃ ), and nitrides of calcium and niobium are calcium nitride (Calcium nitride, chemical formula Ca ₃ N ₂ ) and tantalum nitride (Strontium nitride, chemical formula Sr ₃ N ₂ ).

Preferably, the calcium atom in the calcium source: a germanium atom in the germanium source: an aluminum atom in the aluminum source: a germanium atom in the germanium source: a molar ratio of germanium atoms in the germanium source is 0.01 to 0.999:0 ～0.99:0.95～1:1:0.002～0.02; more preferably, the calcium atom in the calcium source: 锶 atom in the lanthanum source: aluminum atom in the aluminum source: 矽 atom in the 铕 source: in the source The molar ratio of germanium atoms is 0.018 to 0.993: 0 to 0.972: 0.95 to 1:1: 0.002 to 0.016. That is, the amount of calcium atom in the calcium source is in the range of 0.018 to 0.993, and the amount of the molar atom in the germanium source is in the range of 0 to 0.972. The amount of the aluminum atom in the range of 0.95 to 1, and the amount of the ruthenium atom in the source is in the range of 0.002 to 0.016.

The source of oxygen in the phosphor of the present invention may be provided by an aluminum source, a cerium source, a cerium source, a calcium source or a cerium source. Preferably, the starting material may further comprise an oxygen source, the oxygen source acting to provide a source of oxygen in the phosphor. In a specific example of the present invention, the oxygen source is alumina (chemical formula Al ₂ O ₃ ) or cerium oxide. Preferably, the oxygen atom in the oxygen source is from 0 moles to 0.3 moles, based on 1 mole of helium atoms in the source. More preferably, the oxygen source is used in an amount ranging from 0 moles to 0.075 moles.

The higher the purity of each component in the phosphor starting material, the better, preferably 2N or more; more preferably 3N (99.9%) or more. In order to obtain a high-luminance phosphor, impurities in the phosphor starting material or contaminants during the treatment should be as small as possible, in particular, iron, cobalt, nickel, fluorine, boron, When a large amount of elements such as chlorine or carbon are present, the luminous efficiency of the phosphor is suppressed. Therefore, a higher purity raw material can be selected and the synthesis step can be controlled to avoid contamination, such that the content of the elements of iron, cobalt, nickel, fluorine, boron, chlorine or carbon is less than 1000 ppm, respectively.

The particle size and shape of the obtained phosphor will vary depending on the particle size and shape of each component in the phosphor starting material. Therefore, the particle size of each component in the phosphor starting material is It is not particularly limited as long as the final obtained phosphor conforms to the desired particle size. Preferably, the particle size of each component in the phosphor starting material is from the viewpoint of promoting the reaction. The particle size of each component in the phosphor starting material is mainly microparticles.

Since each component in the phosphor starting material is more susceptible to moisture and is easily oxidized, when the components in the starting material (such as Ca ₃ N ₂ , Sr ₃ N _{2 ,} etc.) are weighed and mixed, It is appropriate to operate in a glove box in an inert gas atmosphere, and it is preferable to use a gas which is sufficiently dehydrated by the inert gas. The mixing method of the phosphor starting material may be a dry method (such as a dry ball milling method) or a wet method (such as a wet ball milling method), and the like, and is not limited to a single mode. As the mixing device, a device generally used such as a ball mill or a mortar can be used.

The position at which the adhesive is applied to the main body and the position of the closure member are not particularly limited, and the correspondence between the main body and the size of the closure member can be regarded, and the adhesive can be heated to form a uniform dense structure. The body can be tightly coupled to the closure without a gap. For example, when the body is similar in size to the closure, the adhesive may be applied to the top edge of the body and/or the contact portion of the closure corresponding to the top edge of the body, or the closure When it is larger than the main body, the adhesive may be applied to the side wall of the main body and/or the contact portion of the closing member corresponding to the side wall position of the main body.

The adhesive agent is not particularly limited, and functions to form a dense structure when heated, and the main body and the closure member are bonded without a gap, and the fired container is in an airtight state, thereby improving the burning. The airtightness of the container is such that the chamber of the main body is isolated from the outside, and further vaporization of the components in the phosphor starting material or the phosphor starting material in the firing process is contaminated or Contamination of other impurities (such as oxygen) results in the inability to form the desired phosphor in a predetermined ratio. Preferably, the binder comprises boron nitride, and at least one of an alkaline earth metal nitride or boron monoxide. One. Preferably, the alkaline earth metal nitride comprises tantalum nitride, calcium nitride, tantalum nitride, magnesium nitride, tantalum nitride or the like. Preferably, the total amount of the binder is 1 mol, and the content of boron nitride in the binder is 0.5 mol or more, that is, the binder contains 50 mol% or more of boron nitride. . Preferably, the adhesive contains boron oxide, tantalum nitride and boron nitride of 50 mol% or more. The adhesive is used in such a manner that the main body and the closure member can be uniformly coated, and the amount of use depends on the size of the container, and is not particularly limited.

The baking treatment is not particularly limited, and an object of the invention is to introduce a baking container containing a starting material into a non-oxidizing gas atmosphere and to heat the phosphor starting material to form a reaction. phosphor, ^preferably, a normal pressure sintering method or a gas pressure (pressure in the gas) firing method and the like. The heating method of the baking treatment is not particularly limited, and preferably, the heating method is selected from a metal resistance heating method, a graphite resistance heating method, or the like. The firing treatment is carried out in a non-oxidizing gas atmosphere, for example, in an environment such as nitrogen, hydrogen, ammonia, argon or a mixture of the above gases. The operating temperature of the firing treatment affects the particle size of the phosphor, and the phosphor having a finer particle size can be obtained by firing at a lower temperature, and the phosphor having a larger particle diameter can be obtained by firing at a higher temperature. Preferably, the firing temperature is in the range of 1200 ° C to 2200 ° C. More preferably, the firing temperature is in the range of 1400 ° C to 2000 ° C. Preferably, the temperature rising rate of the firing treatment ranges from 3 ° C/min to 15 ° C/min. The operation time of the baking treatment varies depending on the components in the starting material. Preferably, the operation time of the firing treatment ranges from 1 hour to 12 hours. Preferably, the operating pressure of the baking treatment is performed at 0.5 MPa or less, and more preferably, the firing is performed at 0.1 MPa or less. After the completion of the firing treatment, the phosphor of the present invention can be obtained, and the obtained phosphor can be further pulverized by using a ball mill or an industrial pulverizing machine, and then washed, filtered, dried, or classified. deal with.

By using the adhesive in the above preparation method, the dense agent is formed into a dense structure during the sintering treatment, and then the sintered container is in an airtight state, and the present invention develops a novel red phosphor. It has the formula (I): Ca _a Sr _b Al _c Si _d O _e N _f : Eu _g ... (I)

Where 0 ≦ a < 1, 0 < b < 1, c = 1, 0.8 ≦ d ≦ 1.2, 0 ≦ e ≦ 0.5, 2.5 ≦ f ≦ 3.1, 0.002 ≦ g ≦ 0.020, with the condition that a and b cannot simultaneously Is 0.

Preferably, 0.05 ≦ a ≦ 0.9. Preferably, 0.10 ≦ b ≦ 0.95. Preferably, 0.15 ≦ a + b < 1. Preferably, 0.1 ≦ a/b ≦ 10.

Preferably, 0.9 ≦ d ≦ 1.1.

Preferably, 0≦e≦0.3. Preferably, 2.7 ≦ f ≦ 3.0. When a, b, c, d, e, and f of the phosphor are within the above preferred ranges, the luminance of the light is more excellent. When the value of g is less than 0.002, since the amount of Eu in the luminescent center is small, the luminance of the luminescence is lowered; when the value of g is larger than 0.020, the phenomenon of concentration extinction due to mutual interference between the Eu atoms is caused, so that the luminance is reduced. Preferably, 0.005 ≦ g ≦ 0.016, at which time the luminescent brightness is better.

Preferably, the phosphor further comprises at least one of iron element, cobalt element, nickel element, fluorine element, boron element, chlorine element, and carbon element, and the content of each element is 1000 ppm or less.

Preferably, the phosphor further comprises a magnesium element and/or a strontium element, which can increase the luminosity of the red phosphor, wherein the phosphor contains magnesium in a range of 20 ppm to 1500 ppm, or 钡The content ranges from 40 ppm to 5000 ppm.

Referring to FIG. 1, the luminance and chromaticity of the phosphor of the present invention can be measured by a luminance measuring device, which includes a black box 11, a sample slot 12, a light source 13, and a light. a guiding tube 14, a mirror 15 and a luminance meter 16 (label: TOPCON, model: SR-3A), wherein the sample tank 12 is placed in the housing 11, the light source 13 is disposed perpendicular to the sample The groove 12 is higher than the sample tank 12 by about 5 cm. The light guiding tube 14 has a diameter of about 2 cm and is disposed at an angle of 45 with the light source 13. The mirror 15 is disposed in the light guiding tube 14. And the distance from the sample slot 12 is about 8 cm, and the distance between the luminance meter 16 and the mirror 15 is about 40 cm. When the sample tank 12 is filled with the phosphor and irradiated with the light source 13, the firefly The fluorescent light emitted by the light body is guided to the luminance meter 16 through the action level of the light guiding tube 14 and the mirror 15, and the field 1° mode can be used to detect the fluorescent body emitted by the light source. Fluorescent brightness and chromaticity.

The comparison of the brightness level needs to be meaningful under the same chromaticity value, and the so-called chromaticity value is the same as the x chromaticity coordinate and the y chromaticity coordinate difference within ±0.002, respectively. Preferably, the relative luminance of the red phosphor of the present invention ranges from 55 units to 235 units, and the relative luminance of the red phosphor of the present invention is from 1 unit to 235 units, which is the same as that of the prior art. The relative luminance of the red phosphor (as in the comparative example of the present invention) is about 71 units to 99 units, and it is understood that the phosphor of the present invention has high luminance characteristics under the same chromaticity value, for example, the third embodiment of the present invention and comparison The CIE 1931 chromaticity coordinates (x, y) of the light emitted by the phosphor produced in Example 2 are (0.654, 0.344 ± 0.002), and the luminances are 114 units and 74 units, respectively, which can explain the red color of the present invention. The phosphor has high luminance characteristics, and is applied to the light-emitting device in the subsequent application, so that the light-emitting device has high luminous efficiency.

In the prior art, when the red phosphor of the same system is excited by light having a wavelength of 450 nm to 460 nm, the CIE 1931 chromaticity coordinate (x, y) of the emitted light ranges from 0.617 ≦ x ≦ 0.6699, 0.3263 ≦ y ≦. 0.382, in contrast, the light emitted by the red phosphor of the present invention has a wide chromaticity value, and the CIE 1931 chromaticity coordinate (x, y) of the emitted light ranges from 0.588 ≦ x ≦ 0.683. 0.315≦y≦0.409. Preferably, when the red phosphor of the present invention is irradiated with light having a wavelength of 455 nm, the red phosphor emits light at a CIE 1931 chromaticity coordinate (x, y) ranging from 0.670 ≦ x ≦ 0.683, 0.315 ≦. Y≦0.326, the range is more biased to the red area on the CIE 1931 chromaticity diagram, which is beneficial for subsequent applications on the illuminating device, and can be combined with the illuminating element and/or other phosphor to achieve better color saturation and better The color rendering property provides different choices in the industry. For example, in the first embodiment and the fourteenth embodiment of the present invention, when the red phosphor is irradiated with light having a wavelength of 455 nm, the red phosphor emits light at CIE. The 1931 chromaticity coordinates (x, y) are (0.674, 0.324) and (0.680, 0.317), respectively, which are indeed more reddish on the CIE 1931 chromaticity diagram. Generally, as the amount of strontium added increases, the luminance of the phosphor can be increased, and the y value of the light emitted by the phosphor in the CIE 1931 chromaticity coordinate is also increased, so that the light emitted by the phosphor deviates from the chromaticity coordinate. The red area in the middle, while the increase in the amount of yttrium increases the y value of the light emitted by the phosphor in the chromaticity coordinates, so that the light emitted by the phosphor is biased toward the red area in the chromaticity coordinates, but Resulting in a decrease in the luminance of the phosphor, but the phosphor of the present invention may have a lower y value and at the same time have a high luminance compared to a conventional or commercially available system phosphor, representing the phosphor of the present invention. The emitted light is more biased toward the red region in the chromaticity coordinates and has a longer wavelength of illumination, which not only meets the needs of the industry for long-wavelength phosphors, but also meets the demand for high-saturation and high-luminance red phosphors. .

When the phosphor of the present invention is used in the form of a powder, since the luminescence of the phosphor mainly occurs on the surface of the powder, if the average particle diameter (D ₅₀ ) is 30 μm or less, the powder can be improved per Surface area per unit weight to avoid a decrease in brightness. Further, when the phosphor is bonded to the light-emitting element, the density per unit area of the phosphor powder applied to the light-emitting element can be increased, and the luminance can be prevented from being lowered. If the average particle diameter is 1 μm or less, the luminous efficiency is improved. Getting worse. Preferably, the phosphor has an average particle size ranging from 1 μm ≦ D ₅₀ ≦ 30 μm. More preferably, the phosphor has an average particle size ranging from 3 μm ≦ D ₅₀ ≦ 25 μm.

The composition of the phosphor obtained by the method of the present invention was analyzed, and the values of a, b, d, e and f representing the content of each element were found, compared with the values of a, b, d, e and f in the composition formula of the feed. There are only a few slight deviations. This phenomenon is considered to be caused by a small amount of components decomposing or not entering the crystal lattice of the phosphor during the firing process, or being washed by water, or due to analysis errors. In particular, the deviation of the e value may be caused by the oxygen attached to the surface of each component in the phosphor starting material, or during the weighing of the phosphor starting material, during mixing, and during the firing process. Oxygen formed by oxidation of the surface of each component in the phosphor starting material or moisture or oxygen adsorbed on the surface of the formed phosphor after the firing treatment. Further, when the firing treatment is carried out in an atmosphere containing nitrogen gas and/or ammonia gas, oxygen in each component of the starting material may be removed and replaced by nitrogen, and the value of e may be slightly deviated.

In summary, the present invention can prevent the vaporization of the components in the phosphor starting material or the starting material of the phosphor by applying the adhesive to at least one of the main body and the closure. It is not contaminated by impurities or other impurities (such as oxygen) during the firing process, which makes it impossible to form the desired phosphor in a predetermined ratio, so that the expected composition ratio cannot be formed into the crystal lattice of the phosphor, and the burning is accurately controlled. The composition to the ideal lattice allows the phosphor to have a higher luminance, and the calcium and the calcium are an easily vaporizable element, and the amount of the presence thereof has a significant influence on the luminance of the luminescence, and the preparation method of the present invention The use of the adhesive allows the firing container to be in an airtight state, and it is more effective to promote an easily vaporizable element (for example, strontium element, calcium element) to be effectively combined with each element to form an optimized phosphor composition. The actual composition of the obtained phosphor is not much different from the composition of the feed, which not only reduces the cost, but also obtains a phosphor having high luminance characteristics, and indeed achieves the effect of the present invention. Furthermore, the chromaticity and high luminance of the light emitted by the phosphor of the present invention are not obtained by the red phosphor of the same system in the prior art, and even if the red phosphor of the same system in the prior art is issued The chromaticity value of the light is the same as that of the red phosphor of the present invention, and it is also incapable of the composition of the phosphor of the present invention or the characteristic of high luminance. Although the inventors are currently unable to determine the increase in the brightness of the light emitted by the phosphor and the cause of the change in chromaticity, the inventors speculate that the entry of the contaminant and the starting material are isolated due to the limitation of the airtightness of the firing vessel. Volatilization, so the crystal structure of the phosphor is relatively complete, the lattice defects are less than the red phosphor of the same system in the prior art, and the energy transfer efficiency is higher, so that the phosphor has higher luminous efficiency and better luminance. Moreover, the crystal field around the Eu element in the red phosphor of the present invention should be different from the crystal field around the Eu element in the red phosphor of the same system as in the prior art, and the average of the Eu element and the N element in the phosphor of the present invention. The distance between the Eu element and the N element in the red phosphor of the same system as in the prior art is longer, and the longer average distance causes the excitation energy level to change. When the blue light is the excitation light source, the blue light band can be effectively absorbed, and then The luminance of the phosphor is increased, so that the luminance of the red phosphor of the present invention is higher than that of the red phosphor of the same system, and the range of the chromaticity of the luminescence is wider than that of the red phosphor of the same system. .

The phosphor of the present invention is suitable for use in a fluorescent display tube (VFD), a field emission display (FED), a plasma display (PDP), a cathode ray tube (CRT), a light emitting diode (LED), and the like.

The light-emitting device of the present invention comprises a light-emitting unit comprising a light-emitting element and a red phosphor as described above. Wherein, the phosphor is excited by the light emitted by the illuminating element and emits red light different from the excitation light.

Preferably, the light-emitting element may be a semiconductor made of zinc sulfide or gallium nitride, and more preferably, gallium nitride is used in terms of light-emitting efficiency. The gallium nitride can be formed on the substrate by a method such as metalorganic chemical vapor deposition (MOCVD) or hydride vapor phase epitaxy (HVPE), wherein In _α Al _β Ga _1-α-β N ( The light-emitting elements formed by 0≦α, 0≦β, α+β<1) are optimal.

Preferably, the light-emitting element in the light-emitting device emits light having a wavelength of 300 nm to 550 nm. More preferably, light having a wavelength of from 330 nm to 500 nm is emitted.

Referring to FIG. 2, an embodiment of a light emitting device of the present invention includes a light emitting unit 21, a phosphor layer 22, and an encapsulation layer 23.

The illuminating unit 21 includes a pedestal 211 that is electrically conductive and has a concave bearing surface 212, a light-emitting element 213 disposed on the concave-type bearing surface 212 and electrically connected to the pedestal 211, and a light-emitting element 213 A connecting wire 214 and a wire 215 electrically connected to the connecting wire 214; wherein the base 211 and the wire 215 can cooperate with externally providing electric energy to the light emitting element 213, and the light emitting element 213 can convert electrical energy into light energy. Issued outward. In this embodiment, a commercially available light-emitting element 235 (Intron: Kelly Optoelectronics) of InGaN is bonded to the concave bearing surface 212 of the base 211 by a conductive silver paste (Model: BQ6886, manufacturer: UNINWELL). Then, the connection line 214 and the wire 215 electrically connected to the light-emitting element 213 are extended from the top surface of the light-emitting element 213.

The phosphor layer 22 covers the light emitting element 213. The phosphor 221 included in the phosphor layer 22 is converted to emit light different from the wavelength of the excitation light after being excited by the light emitted from the light-emitting element 213. In the embodiment, the phosphor layer 22 is The polydecaneoxy resin containing the phosphor 221 is coated on the outer surface of the light-emitting element 213, and is formed by drying and hardening.

The encapsulation layer 23 covers the pedestal 211 of the portion of the light-emitting unit 21, the connection line 214, a portion of the wire 215, and the phosphor layer 22.

In the light-emitting device of the present invention, in addition to the use of the phosphor of the present invention alone, it can be used in combination with a phosphor having other light-emitting characteristics to constitute a light-emitting device capable of emitting a desired color.

For example, an ultraviolet light-emitting element of 330 nm to 420 nm, a phosphor emitting blue color of 420 nm to 500 nm (for example, BaMgAl ₁₀ O ₁₇ :Eu), and a green body emitting green light of 500 nm to 570 nm (for example, β-Sialon Firefly) A light-emitting device is prepared by combining the light body and the phosphor of the present invention. When the ultraviolet light emitted by the light-emitting element is irradiated to the phosphors, red light, green light, and blue light are respectively emitted, and the light is mixed with the ultraviolet light of the light-emitting element to become a white light-emitting device (such as a lighting fixture, Light-emitting diodes, etc.).

Further, for example, a light-emitting device is prepared by combining a blue light-emitting element of 420 nm to 500 nm, a phosphor emitting yellow light of 550 nm to 600 nm (such as Y ₃ Al ₅ O ₁₂ :Ce), and a phosphor of the present invention. When the blue light emitted by the light-emitting element is irradiated to the phosphors, red light and yellow light are respectively emitted, and the light is mixed with the blue light of the light-emitting element to become a white light-emitting device (such as a lighting fixture or a light-emitting diode). Wait).

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

<Example> [Example 1]

Weighing 0.277 moles of calcium (Ca ₃ N ₂ ) compound, 0.054 mole of strontium nitride (Sr ₃ N ₂ ) compound, 1 mole of aluminum nitride (AlN, purity 3N), 0.333 mole Cerium nitride (Si ₃ N ₄ , purity 3N) and 0.004 moles of cerium oxide (Eu ₂ O ₃ , purity 4N) were mixed in a glove box using a mortar under a nitrogen atmosphere to form a phosphor starting material. .

The phosphor starting material is placed in a firing container made of boron nitride, and a binder mixed with boron nitride, tantalum nitride and boron oxide in a weight ratio of 10:1:1 is applied to the sintered container. a top edge of the body and a contact portion of the closure member corresponding to a top edge position of the body, and the top surface of the sealing member of the firing container is pressed with a 500 gram boron nitride plate, and then the firing container containing the starting material is Placed in a high-temperature furnace containing high-purity nitrogen gas at a flow rate of 80 liters/min, heated to 1800 ° C at a temperature increase rate of 10 ° C/min, and maintained at 1800 ° C for 12 hours, and the operating pressure of the high-temperature furnace was maintained at 0.1 MPa for firing. After calcination, the temperature is lowered to room temperature according to a temperature decreasing rate of 10 ° C/min, and the phosphor is obtained by a step of pulverization, ball milling, water washing twice, filtration, drying, and classification.

The phosphor was analyzed by a nitrogen oxide analyzer and an inductively coupled plasma atomic emission spectrometer, and its composition was Ca: 22.33 wt%, Sr: 8.96 wt%, Al: 18.77 wt%, Si: 19.49 wt%, and Eu: 0.85. Wt%, N: 27.92 wt%, O: 1.69 wt%. From the above results, the chemical formula of the phosphor was calculated to be Ca _0.801 Sr _0.147 Al ₁ Si _0.998 N _2.866 O _0.152 :Eu _0.008 . The average particle diameter (D ₅₀ ) of the phosphor was 7.5 μm.

[Embodiment 2]

Example 2 was prepared in the same manner as in Example 1 except that Ca ₃ N ₂ , Sr ₃ N ₂ , AlN, Si ₃ N ₄ , Al ₂ O ₃ and Eu ₂ O were changed. The amount of ₃ used. These amounts were prepared in Table 1. The phosphor was analyzed by a nitrogen oxide analyzer and an inductively coupled plasma atomic emission spectrometer. The obtained chemical formula was calculated to be Ca _0.625 Sr _0.2972 Al ₁ Si _0.997 N _2.851 O _0.171 :Eu _0.008 .

[Examples 3 to 15]

In Examples 3 to 15, the phosphor was prepared in the same manner as in Example 1, except that Ca ₃ N ₂ , Sr ₃ N ₂ , AlN, Si ₃ N ₄ , Al ₂ O ₃ and Eu were changed. ₂ O ₃ usage. These amounts were prepared in Table 1. At the same time, the phosphors of the examples were subjected to various test items, and the results obtained are shown in Table 2.

[Comparative Examples 1 to 7]

Comparative Examples 1 to 7 were prepared in the same manner as in Example 1 except that the use of Ca ₃ N ₂ , Sr ₃ N ₂ , AlN, Si ₃ N ₄ and Eu ₂ O ₃ was changed. The amount and the firing conditions were as follows. In Comparative Examples 1 to 5, the firing treatment was carried out under non-airtight conditions. These amounts were prepared in Table 1. At the same time, the phosphors of the comparative examples were subjected to various detection items, and the results obtained are shown in Table 2.

[Evaluation Project] 1. Luminance and chromaticity coordinates: illuminate with an LED light source with a wavelength of 455 nm and measure using the illuminance measuring device shown in Fig. 1. The luminance value measurement difference is within ±0.3%, and the chromaticity value is measured and measured. Within ±0.0005%. The phosphoric acid of each of the sulfates of Examples 1 to 15 and Comparative Examples 1 to 7 was filled and flattened to be uniformly distributed in the sample tank for measurement. 2. Analysis of the constituent elements of the phosphor: 2-1 Inductively coupled plasma atomic emission spectrometer (manufactured by Jobin YVON, model ULTIMA-2) analysis:

0.1 g of the phosphors of Examples 1 to 15 and Comparative Examples 1 to 7 were weighed in a platinum crucible, and 1 g of sodium carbonate (Na ₂ CO ₃ ) was added thereto to be uniformly mixed, and then melted in a high-temperature furnace at 1200 ° C. (Temperature conditions: heating from room temperature for 2 hours to 1200 ° C, constant temperature at 1200 ° C for 5 hours), to be cooled after cooling and adding 25 ml of 36 wt% hydrochloric acid, and then placed on a hot plate to dissolve at 300 ° C to clarify . After heating, it was cooled and placed in a 100 ml dosing bottle, and pure water was added to the mark, and then measured.

2-2 nitrogen oxide analyzer (manufactured by Horiba, model EMGA-620W) analysis:

20 mg of the phosphors of Example 1 and Example 2 were placed in a tin capsule and placed in a crucible for measurement.

3. D ₅₀ average particle size analysis: analysis using a Beckman Coulter Multisizer-3 instrument, measured by Coulter method. D ₅₀ indicates that in this test, the cumulative volume of particles having a particle diameter smaller than this value accounts for 50% of the total volume of the particles.

As is apparent from the experimental results in Table 2, the present invention allows the firing container to be in an airtight state by the use of an adhesive, and an optimized phosphor composition can be obtained, such as the red phosphors of Example 5 and Comparative Example 3. Although having the same composition formula (Ca _0.20 Sr _0.792 Al ₁ Si ₁ O _0.012 N _2.995 :Eu _0.008 ), the chemical formula of the red phosphor of Example 5 is not significantly different from the Sr of the composition of the feed (only 9.7) In contrast, the chemical formula of the red phosphor of Comparative Example 3 differs greatly from the Sr in the composition formula (58.4%), and the chromaticity value of the light emitted by the red phosphor of Example 5 (0.634, 0.364) And the luminance (158 units) is a chromaticity value (0.640, 0.355) and a luminance (79 units) of light emitted from the red phosphor of Comparative Example 3; further, compared with the same chromaticity value In the red phosphor of the same system in the prior art, the light emitted by the red phosphor of the present invention has a high luminance, and the light emitted by the red phosphors of Example 3 and Comparative Example 2 has the same chromaticity. Value (0.654, 0.342 ± 0.002), but the light emitted by the red phosphor of Example 3 has a luminance of 114 units and Comparative Example 2 The light emitted by the red phosphor having a luminance of 74 units. In summary, it is stated that the red phosphor of the prior art system under the same composition formula is unable to achieve the chromaticity value and high luminance characteristic of the light emitted by the red phosphor of the present invention, and even if The red phosphor of the same system of the prior art is also different from the actual composition of the red phosphor of the present invention, and does not have high luminance characteristics. Meanwhile, the light emitted by the red phosphor of Embodiment 14 of the present invention can have a high x value (0.680) and a low y value (0.317) and has high luminance characteristics, which can satisfy the industry for high saturation and high. The need for a luminance phosphor. The chromaticity coordinates (x, y) of the light emitted by the red phosphors of Examples 1 and 14 are (0.674, 0.324) and (0.680, 0.317, respectively) are red phosphors of the same system in the prior art. Unable to reach. Moreover, the test results of the red phosphors of Comparative Examples 6 and 7 further prove that the elements in the phosphor such as Eu need to be adjusted in the range of elements in the phosphor of the present invention, so as to satisfy the requirement of high luminance.

In summary, the preparation method of the present invention utilizes the use of an adhesive, so that each element can be effectively combined in a predetermined ratio to form an optimized phosphor composition, and the chemical formula and composition of the obtained phosphor are composed. The difference in formula is not large, not only can reduce the cost, but also obtain a phosphor having high luminance characteristics, so that the chromaticity and high luminance characteristic of the light emitted by the phosphor of the present invention are the same system of the prior art. The phosphor can not be achieved, and the phosphor helps to enhance the color rendering and color saturation of the white light emitted by the white light emitting device, and can provide different choices in the industry, so that the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

11. . . Box

12. . . Sample slot

13. . . light source

14. . . Light guiding tube

15. . . Reflector

16. . . Luminometer

twenty one. . . Light unit

211. . . Pedestal

212. . . Concave bearing surface

213. . . Light-emitting element

214. . . Cable

215. . . wire

twenty two. . . Fluorescent layer

221. . . Phosphor

twenty three. . . Encapsulation layer

Figure 1 is a schematic view showing the state of use of the glow measuring device;

Figure 2 is a perspective view of an embodiment of a light emitting device of the present invention.

Claims (20)

A method for accurately controlling the proportion of a fired structural component of a fired body, comprising the steps of: providing a firing vessel comprising a body having a chamber and a closure for closing the chamber; and a phosphor The starting material is placed in the chamber of the main body; at least one of the main body and the sealing member is applied to the main body and the sealing member; and after the firing container is fired in a non-oxidizing gas atmosphere, Obtain a phosphor. The method of claim 1, wherein the adhesive forms a dense structure during the firing treatment. The method of claim 1, wherein the binder binds the body to the closure without a gap and causes the container to be in an airtight state during the firing treatment. The method of claim 1, wherein the adhesive comprises at least one selected from the group consisting of boron nitride, and an alkaline earth metal nitride or boron oxide. The method according to claim 4, wherein the content of the boron nitride in the adhesive is 0.5 mol or more based on the total amount of the adhesive. The method according to claim 1, wherein the operating pressure of the baking treatment is in a range of 0.5 MPa or less. The method of claim 1, wherein the firing temperature is in the range of 1200 ° C to 2200 ° C. The method according to claim 1, wherein the temperature increase rate of the baking treatment is in the range of 3 ° C / min to 15 ° C / min. The method according to claim 1, wherein the operation time of the baking treatment ranges from 1 hour to 12 hours. The method of claim 1, wherein the phosphor starting material comprises at least one of an aluminum source, a germanium source, a germanium source, and a calcium source or a germanium source. The method according to claim 10, wherein the aluminum source, the germanium source, the germanium source, the calcium source and the germanium source are aluminum nitride, germanium nitride, germanium oxide, and calcium nitride, respectively. And niobium nitride. The method according to claim 10, wherein the calcium atom in the calcium source: the germanium atom in the germanium source: the aluminum atom in the aluminum source: the germanium atom in the germanium source: the germanium atom in the germanium source The molar ratio is 0.01~0.999:0~0.99:0.95~1:1:0.002~0.02. A phosphor produced by the method of any one of claims 1 to 12. A phosphor having the formula (I): Ca _a Sr _b Al _c Si _d O _e N _f :Eu _g (I) wherein 0≦a<1,0<b<1, c=1, 0.8≦ d≦1.2,0≦e≦0.5, 2.5≦f≦3.1, 0.002≦g≦0.020, provided that a and b cannot be 0 at the same time, and the phosphor is emitted when excited by light with a wavelength of 455 nm. The CIE1931 color coordinate (x, y) of the light satisfies the following relationship: x = [(-0.1059b ³ + 0.068b ^{2 -} 0.06b) + (2152.8g ³ -309.2g ² + 8.2943g) + 0.6324] ± 0.01 ;y=[(0.1295b ³ -0.0968b ² +0.0702b)+(-3299.2g ³ +311.08g ² -7.9266g)+0.3621]±0.01. The phosphor according to claim 14, wherein the reflectance of the barium sulfate after being reflected by light having a wavelength of 455 nm is 1 unit, and the relative luminance of the phosphor ranges from 55 units to 235 units. The phosphor according to claim 14, wherein the CIE 1931 chromaticity coordinate (x, y) of the light emitted by the phosphor ranges from 0.670 ≦ x ≦ 0.683, 0.315 ≦ y ≦ 0.326. The phosphor according to item 14 of the patent application, wherein 0.1 ≦b ≦ 0.95. The phosphor according to item 14 of the patent application, wherein 0.005 ≦g ≦ 0.016. A light-emitting device comprising: a light-emitting unit comprising a light-emitting element; and a red phosphor as described in claim 14. The illuminating device according to claim 19, wherein the illuminating element emits a wavelength in the range of 300 nm to 500 nm.