KR101405596B1 - New composition of aluminum silicate phosphor and preparing method thereof - Google Patents

Abstract

The present invention relates to an aluminum silicate-based fluorescent material and a method for producing the same. More particularly, the present invention relates to an aluminum silicate-based fluorescent material which excites at a wavelength of 250 to 500 nm and has emission characteristics at a wavelength of 400 to 800 nm, A method for producing the same, and a light emitting device comprising an aluminum silicate-based phosphor represented by the following formula (1).
M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)
In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0? x? 1; y is 0 < y &lt; 0.5.

Description

TECHNICAL FIELD The present invention relates to an aluminum silicate phosphor and a method for producing the phosphor,

The present invention relates to an aluminum silicate-based fluorescent material and a method for producing the same. More particularly, the present invention relates to an aluminum silicate-based fluorescent material which excites at a wavelength of 250 to 500 nm and has emission characteristics at a wavelength of 400 to 800 nm, A method for producing the same, and a light emitting device comprising an aluminum silicate-based phosphor represented by the following formula (1).

M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)

In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0? x? 1; y is 0 < y &lt; 0.5.

White light emitting diodes (white LEDs) are one of the next-generation light emitting device candidates that can replace fluorescent light, which is one of the most typical conventional lighting.

Light emitting diodes have less power consumption than conventional light sources, and unlike fluorescent lamps, they do not contain mercury and can be said to be environmentally friendly. In addition, it has a longer life span and faster response time than conventional light sources.

There are three methods for manufacturing a white light emitting diode: (1) a method of realizing white light by combining red, green, and blue LED chips, (2) a method of implementing a white light by applying a yellow phosphor to a blue LED chip, (3) A method of implementing white light by combining red, green, and blue LED chips on an ultraviolet (UV) LED chip.

In order to realize white light by combining red, green, and blue LED chips, different films such as InGaN, GaN, GaAs, and ZnO must be made. Such a manufacturing method requires manufacturing different light emitting diodes, . In addition, when the red, green, and blue LED chips are combined, the driving voltage of each LED chip is different. Therefore, there arises a problem of complexity of the manufacturing process and restriction of design due to the complicated structure of the respective circuits.

The method of applying a yellow phosphor to a blue LED chip to realize white light is currently the most widely used and is the most representative method of realizing white light by using a light emitting diode. Currently, the most widely used white light emitting diodes are manufactured by applying YAG: Ce phosphor, which is a yellow phosphor, to a blue LED chip. In the case of the method of combining white LED with blue LED chip and yellow phosphor, it is difficult to find a phosphor having an excitation wavelength of 450 nm and an excitation wavelength of 450 nm in light emitting diode. Therefore, Follow. When a yellow phosphor is used as a phosphor excited by a blue LED chip, there is a disadvantage that a color rendering index (CRI) is lowered due to weak light emission in a red region. In addition, since the blue light source changes according to the driving voltage in the above method, the color coordinate becomes unstable.

The above problems can be solved in the case of combining a red, green, and blue phosphors in an ultraviolet LED chip or a method of implementing white light using phosphors having a full width half maximum (FWHM) emission spectrum. When a red phosphor, a green phosphor, and a blue phosphor are applied to a long wavelength ultraviolet light emitting diode, or a yellow phosphor having a wide half width, white light similar to solar light having a high color rendering index can be produced. Therefore, there is an urgent need to develop phosphors having high color rendering and high efficiency which are excited by such ultraviolet and blue light emitting diodes.

As a prior art related to the present invention, Korean Patent No. 10-0621153 discloses a silicate phosphor for a white light emitting diode device represented by the following Chemical Formula 1, a process for producing the same, and a white light emitting diode device using the same.

Sr _X Ba _2-X SiO ₄ : Eu ????? (1)

(In the above, X is 1.00? X? 1.96.)

Also, in Korean Patent Publication No. 2003-0051345, a mixture of at least one metal compound selected from the group consisting of silicon oxide having a BET specific surface area of 10 m ² / g or more and Ca, Sr, Ba, Mg, Eu, a method for producing a silicate phosphor comprising a step of, wherein the silicate phosphor, mM1O · nM2O · 2SiO least one element selected from, M1 is a group consisting of Ca, Sr and Ba of ₂ (wherein, M2 is at least one element selected from the group consisting of Mg and Zn, m is from 0.5 to 3.5, and n is from 0.5 to 2.5, and Eu and Mn as the activator are selected from the group consisting of And at least one silicate phosphor.

However, since the present invention and the phosphors of the prior art are different from each other in major components and technical features, the present invention and the prior art are inventions having different compositions.

The present invention addresses the problems of low color rendering and brightness in conventional phosphors excited by ultraviolet and blue light emitting diodes, and is excited by a wavelength of 250 to 500 nm represented by ultraviolet and blue light emitting diodes, , A method for producing the same, a light-emitting device including the aluminum silicate-based fluorescent material, and a display device including the light-emitting device including the aluminum silicate-based fluorescent material .

The present invention relates to an aluminum silicate-based phosphor which is excited at a wavelength of 250 to 500 nm represented by ultraviolet and blue light emitting diodes and has a luminescence property at a wavelength of 400 to 800 nm and is represented by the following formula (1) 1), and a display device containing a light-emitting device comprising an aluminum silicate-based phosphor represented by the following formula (1).

M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)

In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0? x? 1; y is 0 < y &lt; 0.5.

The phosphor represented by the following formula (1) of the present invention is produced by a heat treatment process at a temperature of 1200 ° C or higher, using M _{1 + xy} Al _{1 + x} Si _2-x O ₆ as a matrix and Q as an activator and / , It is possible to excite at a wavelength of 250 to 500 nm and exhibit an emission spectrum of a wide wavelength ranging from 400 to 800 nm.

The phosphor represented by the following formula (1) of the present invention can produce an aluminum silicate-based phosphor using Q as an activator and / or a negative activator, and obtains a phosphor emitting light by using ultraviolet and blue light emitting diodes as an excitation energy source .

The phosphor of the present invention can be applied to a light emitting device, preferably a white light emitting diode, coupled to ultraviolet and blue light emitting diodes.

M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)

In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0? x? 1; y is 0 < y &lt; 0.5.

1 is a view showing a process for producing the aluminum silicate phosphor of the present invention.
FIG. 2 is a graph showing the emission spectrum of a phosphor obtained by exciting a phosphor prepared according to the heat treatment temperature in Examples 1-1 to 1-4 with ultraviolet rays of 395 nm. FIG.
3 is a graph showing absorption spectra of the phosphors prepared according to the heat treatment temperatures in Examples 1-1 to 1-4.
4 is a graph showing the XRD diffraction pattern of the phosphor prepared according to the heat treatment temperature in Examples 1-1 to 1-4.
FIGS. 5A and 5B are graphs showing the relationship among the values of K _{1 + xy} Al _{1 + x} Si _{2 -x} O ₈ : Eu ²⁺ _y (x = 0, y = (Eu ^{2 +} _y (y = 0.01 to 0.25)) of the activator Eu ²⁺ in the aluminum silicate phosphor of 0.01 to 0.25.
6a and 6b are graphs showing the relationship between the K _{1 + x y} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0, 0.2, 0.6, 1, y = 0.1) with a wavelength of 410 to 800 nm using a 450 nm filter under excitation of a 395 nm wavelength, and FIGS. 6A and 6B are graphs showing emission spectra of the aluminum silicate phosphors The aluminum silicate fluorescent material having the composition of K _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (x = 0, y = 0.1) in 6b is A, K _{1 + xy} Al _{1 + x} Si _{2-x ^{O 6: Eu 2+ y (x}} = 0.2, y = 0.1) the composition of aluminum silicate phosphors _{B, K 1 + xy Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0.6, y = 0.1) composition of the aluminum silicate fluorescent material is represented by C, K _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (x = 1, y = 0.1)
7 is a graph showing the relationship between K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.07 Mn ²⁺ _0.03 (B) of the composition of K _0.9 AlSi ₂ O ₈ : Ce ³⁺ _0.1 prepared in Example 4-2, K of the aluminum silicate fluorescent substance (B) prepared in Example 2-4, (A) which has a composition of _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.1 in terms of a photoluminescence spectrum, which is an emission spectrum at a wavelength of 400 to 800 nm.
FIG. 8 is a graph showing emission spectra (EL intensity) at a wavelength of 350 to 750 nm by exciting the light emitting diode manufactured in Application Example 1 at 3 V and 20 mA at an ultraviolet wavelength.

The present invention shows an aluminum silicate-based phosphor.

The present invention relates to an aluminum silicate-based phosphor represented by the following formula (1).

M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)

In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0? x? 1; y is 0 < y &lt; 0.5.

The aluminum silicate-based phosphor represented by the above formula (1) exhibits a property of exciting at a wavelength of 250 to 500 nm.

The aluminum silicate-based phosphor represented by the above formula (1) exhibits a characteristic of emitting light at a wavelength of 400 to 800 nm.

The aluminum silicate-based phosphor represented by the formula (1) excites at a wavelength of 250 to 500 nm and emits light at a wavelength of 400 to 800 nm.

The size of the aluminum silicate-based phosphor represented by the formula (1) may be 0.5 to 20 탆.

The size of the aluminum silicate-based phosphor represented by the formula (1) may be 1 to 10 탆.

The aluminum silicate-based fluorescent material represented by the formula (1) may have at least one crystal phase selected from among cubic, tetragonal, orthorhombic, and hexagonal.

The present invention shows a method for producing an aluminum silicate-based phosphor.

The present invention relates to a method for producing an aluminum alloy, comprising the steps of: adding aluminum (Al), silica (Si), an alkali metal and an activator to a solvent, Heat treating the dry mixture; And a step of cooling and pulverizing the mixture to a normal temperature after the heat treatment step, thereby producing an aluminum silicate-based phosphor represented by the following formula (1) (see FIG. 1).

M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)

In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0? x? 1; y is 0 < y &lt; 0.5.

In the above, compounds in the form of aluminum (Al), silica (Si), alkali metal and / or activator may be used.

In the above, compounds in the form of aluminum (Al), silica (Si), alkali metal and / or activator in chloride form can be used.

In the above, aluminum (Al), silica (Si), alkali metal and / or activator may be in a hydroxide form.

In the above, aluminum (Al), silica (Si), alkali metal and / or activator may be in the form of a nitrate form.

In the above, aluminum (Al), silica (Si), alkali metal and / or activator may be in the form of carbonates.

As the aluminum (Al), silica (Si), alkali metal and / or activator in the above, compounds in the form of super oxide may be used.

Among the raw material components of the phosphor, any one or more selected from among aluminum nitride (Al (NO ₃ ) ₃ ), aluminum oxide (Al ₂ O ₃ ) and aluminum chloride (AlCl ₃ ) can be used.

Among the raw material components of the phosphor, at least one selected from tetraorthosilicate (TEOS) and meta-sodium silicate (Na ₂ SiO ₃ ) can be used as an example of silica.

Among the raw materials of the phosphor, sodium nitrate (NaNO ₃ ), sodium chloride (NaCl), lithium nitrate (LiNO ₃ ), lithium chloride (LiCl), potassium nitrate (KNO ₃ ), potassium chloride (KCl) may be used.

Active agents from the raw material component of the fluorescent substance in the above is europium chloride (EuCl _3), europium nitrate _{(Eu (NO 3) 3)} , yttrium nitrate _{(Y (NO 3) 3)} , lanthanum nitrate (La (NO _{3 3) 3),} manganese chloride (MnCl _2), manganese nitrate _{(Mn (NO 3) 2)} , kappa nitrate _{(Cu (NO 3) 2)} , any one selected from cerium nitrate (Ce (NO _{3) 3)} Or more can be used.

The solvent may be at least one selected from the group consisting of an alcohol solvent having 1 to 10 carbon atoms, acetone, and water.

As an example of the solvent, methanol may be used.

As an example of the solvent, ethanol may be used.

As an example of the solvent, acetone may be used.

As an example of the solvent, water may be used.

In the above, the raw materials mixed in the solvent and the solvent may be mixed to have a uniform composition using stirring and / or ultrasonic vibration.

The raw material mixed in the solvent and the solvent is mixed with stirring at 100 to 500 rpm for 1 to 24 hours and / or ultrasonic vibration using a ultrasonic oscillator capable of emitting a frequency of 50 to 100 kHz so as to have a uniform composition .

Drying can be done completely at 50-200 &lt; 0 &gt; C until the solvent disappears.

The heat treatment may be carried out at a temperature of 1200 to 1500 ° C for 1 to 10 hours.

The heat treatment may be carried out at a temperature of 1200 to 1500 占 폚 and for 1 to 10 hours under a mixed gas reducing atmosphere in which 75 to 98% by volume of nitrogen, neon or argon and 2 to 25% by volume of hydrogen are mixed.

The heat treatment may be performed by placing the dried mixture in an alumina crucible at a temperature of 1200 to 1500 ° C for 1 to 10 hours.

The heat treatment can be carried out by placing the dried mixture in an alumina crucible for 1 to 10 hours at a temperature of 1,200 to 1,500 DEG C and a mixed gas reducing atmosphere in which 75 to 98% by volume of nitrogen, neon or argon and 2 to 25% have.

After the heat treatment step, the powder is cooled to room temperature and then grinded to obtain a powdery phosphor.

The grinding step may be carried out such that the size of the phosphor is 0.5 to 20 mu m.

The pulverizing step may be carried out such that the size of the phosphor is 1 to 10 mu m.

In the above, the normal temperature means a temperature of 20 to 30 캜, preferably 20 to 25 캜.

The aluminum silicate-based fluorescent material represented by the formula (1) prepared above may have at least one crystal phase selected from cubic, tetragonal, orthorhombic, and hexagonal as a main phase .

The present invention includes a phosphor represented by the above-mentioned formula (1) or a phosphor prepared by the above-mentioned method and containing a phosphor represented by the formula (1).

The light emitting device may include a light emitting layer including a phosphor represented by Formula (1).

The light emitting device may include a light emitting layer in which a phosphor represented by Formula (1) is dispersed in epoxy.

The light emitting device may include a light emitting layer in the form of a film formed by a screen printing method, an inkjet method, or a gravure printing method using the phosphor represented by Formula (1).

The light emitting device may be a white LED including a phosphor represented by Formula (1).

The light emitting diode includes a light source for emitting light, a substrate for supporting the light source, and a molding member molded around the light source, wherein the light emitting diode includes an aluminum A light emitting diode can be constituted by coating a coated phosphor composition for a light emitting element containing epoxy with a silicate-based fluorescent material and a molding member around the light emitting diode chip.

The present invention includes a display device containing a light-emitting element comprising a phosphor represented by the above-mentioned formula (1) or a phosphor prepared by the above-mentioned method and comprising a phosphor represented by the formula (1) .

The light-emitting device contained in the display device may include a light-emitting layer in which a phosphor represented by Formula (1) is dispersed in epoxy.

The light-emitting device contained in the display device includes a film-type light-emitting layer manufactured by a screen printing method, an inkjet method, or a gravure printing method using the phosphor represented by Chemical Formula (1) can do.

The light emitting device contained in the display device may be a white LED including a phosphor represented by Formula (1).

The display device may be an illumination (illumination).

The display device may be a back light and / or a display.

In order to achieve the object of the present invention, the aluminum silicate-based fluorescent material of the present invention and the method for producing the same are provided under various conditions, and it is preferable to provide the aluminum silicate-based fluorescent material and the production method thereof by the above-mentioned conditions.

Hereinafter, the present invention will be described in detail by way of examples, test examples and application examples. However, these are only examples for explaining the present invention in more detail, and the scope of the present invention is not limited thereto.

<Example 1-1> Preparation of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 phosphor according to heat treatment temperature

The aluminum silicate-based phosphor having a composition of M _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Q _y shown in FIG. 1 was prepared by using a manufacturing process of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 phosphor (M _{1 + xy} (K), x = 0, y = 0.05 in an aluminum silicate-based phosphor having a composition of Al _{1 + x} Si _{2 -x} O ₆ : Q _y ).

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 . (2) by dissolving Tetraorthosilicate (TEOS) in 10 ml of ethanol at a 2-x molar ratio ((x = 0, y = x = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred by ultrasonic ultrasonic vibration to obtain a mixture having a uniform composition.

The mixture was completely dried at 120 ° C until the solvent was removed, and then heat-treated at a temperature of 1200 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

<Example 1-2> Preparation of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 phosphor according to heat treatment temperature

An aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 was prepared in the same manner as in Example 1-1, except that the heat treatment temperature was changed to 1300 ° C.

Example 1-3 Preparation of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 Phosphor by Annealing Temperature

An aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 was prepared in the same manner as in Example 1-1 except that the heat treatment temperature was changed to 1400 ° C.

<Example 1-4> Preparation of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 phosphor according to heat treatment temperature

An aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 was prepared using the same method as in Example 1-1 except that the heat treatment temperature was set to 1500 ° C.

&Lt; Test Example 1 >

Each of the K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 aluminum silicate phosphors prepared at different heat treatment temperatures in Examples 1-1 to 1-4 was excited at a wavelength of 395 nm, The emission wavelength was measured using a filter, which is shown in Fig.

As shown in FIG. 2, each of the K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 aluminum silicate phosphors prepared in Examples 1-1 to 1-4 had emission wavelengths in the range of 400 to 800 nm , In particular, in the range of 450 to 550 nm. It was also found that the phosphor prepared by treating the K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 aluminum silicate phosphor with a heat treatment temperature of 1200 to 1400 ° C had better luminescence properties.

&Lt; Test Example 2 &

The absorption spectra of each of the K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 aluminum silicate phosphors prepared by varying the heat treatment temperatures in Examples 1-1 to 1-4 were measured, The results are shown in FIG.

The K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 aluminum silicate phosphor prepared by varying the heat treatment temperature in each of Examples 1-1 to 1-4 as shown in FIG. 3 exhibited absorption The spectrum was high.

&Lt; Test Example 3 > K _0.95 AlSi ₂ O ₆ : Eu ² _0.05 XRD diffraction pattern according to heat treatment temperature of phosphor.

The XRD diffraction pattern of each of the K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 aluminum silicate phosphors prepared by varying the heat treatment temperatures in Examples 1-1 to 1-4 was measured This is shown in FIG.

As shown in FIG. 4, each of the K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 prepared in <Examples 1-1> to <1-4> was subjected to heat treatment at a temperature of 1200 ° C. to 1500 ° C. It was confirmed that the aluminum silicate phosphor formed a single phase. In addition, the single - phase aluminum silicate was formed closer to the K _0.95 AlSi ₂ O ₈ composition as the heat treatment was performed at high temperature.

On the other hand, PDF # 86-1650 described in the lower part of FIG. 4 shows that the aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 prepared in the above <Examples 1-1> to <Example 1-4> , The XRD patterns of the conventional reference samples indicating that the K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 aluminum silicate phosphors prepared in <Examples 1-1> to <1-4> And the pattern of the existing reference sample were matched, it was found that the phosphor composition was well synthesized.

&Lt; Example 1-5 >

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 . (2) by dissolving Tetraorthosilicate (TEOS) in 10 ml of ethanol at a 2-x molar ratio ((x = 0, y = x = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred by ultrasonic ultrasonic vibration to obtain a mixture having a uniform composition.

The mixture was thoroughly dried at 120 ° C until the solvent was gone and heat-treated at a temperature of 1200 ° C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

<Example 1-6> Preparation of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 phosphor according to heat treatment temperature

An aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 was prepared in the same manner as in Example 1-5, except that the heat treatment temperature was changed to 1300 ° C.

<Example 1-7> Preparation of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 phosphor according to heat treatment temperature

An aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 was prepared in the same manner as in Example 1-5, except that the heat treatment temperature was changed to 1400 ° C.

<Example 1-8> Preparation of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 phosphor according to heat treatment temperature

An aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05 was prepared in the same manner as in Example 1-5, except that the heat treatment temperature was set to 1500 ° C.

<Example 2-1> Preparation of aluminum silicate phosphor of K _0.99 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.01)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having the composition of K _0.99 AlSi ₂ O ₈ : Eu ²⁺ _0.01. (2) a solution of tetraorthosilicate (TEOS) in 10 ml of ethanol at a 2-x molar ratio (x) of 1 x x: 1 + xy: y mol ratio = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

<Example 2-2> Preparation of aluminum silicate phosphor of K _0.97 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.03)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.97 AlSi ₂ O ₈ : Eu ²⁺ _0.03 ) Was dissolved respectively in a ratio of 1 + x: 1 + xy: y mol (x = 0, y = 0.03) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

<Example 2-3> Preparation of aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.05)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05. ) Was dissolved in a ratio of 1 + x: 1 + xy: y mol respectively (x = 0, y = 0.05) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 2-4 Aluminum Silicate Phosphor Production of K _0.93 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.07)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.93 AlSi ₂ O ₈ : Eu ²⁺ _0.07 ) Was dissolved in each of 1 + x: 1 + xy: y mol ratios (x = 0, y = 0.07) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 2-5 Preparation of aluminum silicate phosphor of K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.1)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.1 ) Was dissolved in each of 1 + x: 1 + xy: y mol ratios (x = 0, y = 0.1) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 2-6 Preparation of aluminum silicate phosphor of K _0.85 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.15)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.85 AlSi ₂ O ₈ : Eu ²⁺ _0.15. ) Was dissolved in each of 1 + x: 1 + xy: y mol ratios (x = 0, y = 0.15) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 2-7 Preparation of aluminum silicate phosphor of K _0.8 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.20)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.8 AlSi ₂ O ₈ : Eu ²⁺ _0.20. ) Was dissolved respectively in a ratio of 1 + x: 1 + xy: y mol (x = 0, y = 0.20) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 2-8 Preparation of aluminum silicate phosphor of K _0.75 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.25)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.75 AlSi ₂ O ₈ : Eu ²⁺ _0.25. ) Was dissolved in a ratio of 1 + x: 1 + xy: y mol respectively (x = 0, y = 0.25) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

<Test Example 4>

(X = 0, y = 0.01 to 0.25) prepared in the above Examples 2-1 to 2-8 were mixed to prepare a _mixture of K _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y The emission wavelength in the range of 400 to 800 nm under the excitation of the 395 nm wavelength is measured according to the change of the Eu ²⁺ concentration in the aluminum silicate phosphor of 1 to 25 mol% [Eu ²⁺ _y (y = 0.01 to 0.25)], 5a and 5b.

As the Eu ²⁺ concentration increases in the aluminum silicate phosphor of K _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0, y = 0.01 to 0.25) And a central wavelength was observed in the vicinity of 460 to 540 nm.

FIG. 5B shows the change of the emission wavelength according to the Eu concentration in the emission wavelength range of 440 to 560 nm of FIG. 5A.

Example 2-9 Preparation of aluminum silicate phosphor of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.05)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.95 AlSi ₂ O ₈ : Eu ²⁺ _0.05. ) Was dissolved in a ratio of 1 + x: 1 + xy: y mol respectively (x = 0, y = 0.05) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 2-10 Preparation of aluminum silicate phosphor of K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _y (y = 0.1)

(Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were added to 10 ml of water to prepare a phosphor having a composition of K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.1 ) Was dissolved in each of 1 + x: 1 + xy: y mol ratios (x = 0, y = 0.1) to obtain a solution; (2) tetraorthosilicate (TEOS) = 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred with ultrasonic ultrasonic waves to obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 3-1 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0, y = 0.1) aluminum nitrate (1) 10ml of water to produce the phosphor (of Al (NO ₃ ), ₃ ), potassium nitrate (KNO ₃ ), and europium chloride (EuCl ₃ ) were dissolved in a ratio of 1 + x: 1 + xy: y mol respectively (x = 0, y = 0.1) (3) The solution of (1) and the solution of (2) are ultrasonically dissolved in 10 ml of ethanol by dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio (x = 0) And the mixture was stirred to obtain a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 3-2 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0.2, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0.2, y = 0.1) (1) for producing the phosphor of the aluminum in water 10ml nitrate (Al (NO ₃ ), ₃ ), potassium nitrate (KNO ₃ ), and europium chloride (EuCl ₃ ) were dissolved respectively in the ratio of 1 + x: 1 + xy: y mol (x = 0.2, y = 0.1) (3) The solution of the above (1) and the solution of (2) were ultrasonically dissolved in 10 ml of ethanol by dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio (x = 0.2) And the mixture was stirred to obtain a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 3-3 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0.6, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0.6, y = 0.1) (1) for producing the phosphor of the aluminum in water 10ml nitrate (Al (NO ₃ ) _3), potassium nitrate (KNO _3), and europium chloride (a EuCl ₃₎ 1 + x, respectively: 1 + xy: y is dissolved in mol ratio (x = 0.6, y = 0.1 ) to obtain a solution, (2 Dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio (x = 0.6) to 10 ml of ethanol to obtain a solution; (3) dissolving the solution of (1) and the solution of (2) ) To obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 3-4 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 1, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 1, y = 0.1) (1) for producing the phosphor of aluminum nitrate in water, 10ml (Al (NO ₃ ), ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were dissolved respectively in the ratio of 1 + x: 1 + xy: y mol (x = 1, y = 0.1) (3) The solution of (1) and the solution of (2) are ultrasonically dissolved in 10 ml of ethanol by dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio And the mixture was stirred to obtain a homogeneous composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

&Lt; Test Example 5 >

The <Example 3-1> to <Example 3-4> A _{K 1 + xy Al 1 + x} Si 2-x O 6 _{^{prepared: Eu 2+ y (x = 0}} , 0.2, 0.6, 1, y = 0.1) was measured with a 450 nm filter under excitation of 395 nm wavelength, and PL spectra of emission wavelengths in the wavelength range of 410 to 800 nm were measured. The results are shown in FIGS. 6A and 6B, respectively .

As shown in FIGS. 6A and 6B, the aluminum silicate phosphor having a composition of K _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (x = 0, 0.2, 0.6, 1, y = 0.1) x = 0.6. As shown in FIG. 6B, it was found that the wavelength shifts from 480 nm to a long wavelength near 550 nm according to the change of x value.

The aluminum silicate fluorescent material having a composition of K _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (x = 0, y = 0.1) in FIGS. 6A and 6B is A, K _{1 + xy} Al _{1 + x Si 2-x O 6: Eu} 2+ y (x = 0.2, y = 0.1) the composition of aluminum silicate phosphors _{B, K 1 + xy Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0.6, y = 0.1), the aluminum silicate fluorescent material having a composition of C, K _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (x = 1, y = 0.1) .

Example 3-5 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0, y = 0.1) aluminum nitrate (1) 10ml of water to produce the phosphor (of Al (NO ₃ ), ₃ ), potassium nitrate (KNO ₃ ), and europium chloride (EuCl ₃ ) were dissolved in a ratio of 1 + x: 1 + xy: y mol respectively (x = 0, y = 0.1) (3) The solution of (1) and the solution of (2) are ultrasonically dissolved in 10 ml of ethanol by dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio (x = 0) And the mixture was stirred to obtain a homogeneous composition.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 3-6 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0.2, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0.2, y = 0.1) (1) for producing the phosphor of the aluminum in water 10ml nitrate (Al (NO ₃ ), ₃ ), potassium nitrate (KNO ₃ ), and europium chloride (EuCl ₃ ) were dissolved respectively in the ratio of 1 + x: 1 + xy: y mol (x = 0.2, y = 0.1) (3) The solution of the above (1) and the solution of (2) were ultrasonically dissolved in 10 ml of ethanol by dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio (x = 0.2) And the mixture was stirred to obtain a homogeneous composition.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 3-7 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 0.6, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 0.6, y = 0.1) (1) for producing the phosphor of the aluminum in water 10ml nitrate (Al (NO ₃ ) _3), potassium nitrate (KNO _3), and europium chloride (a EuCl ₃₎ 1 + x, respectively: 1 + xy: y is dissolved in mol ratio (x = 0.6, y = 0.1 ) to obtain a solution, (2 Dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio (x = 0.6) to 10 ml of ethanol to obtain a solution; (3) dissolving the solution of (1) and the solution of (2) ) To obtain a mixture having a homogeneous composition.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 3-8 M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Eu ²⁺ _y (x = 1, y = 0.1) Aluminum silicate phosphors

_{K 1 + x-0.1 Al 1} + x Si 2-x O 6: Eu 2+ y (x = 1, y = 0.1) (1) for producing the phosphor of aluminum nitrate in water, 10ml (Al (NO ₃ ), ₃ ), potassium nitrate (KNO ₃ ) and europium chloride (EuCl ₃ ) were dissolved respectively in the ratio of 1 + x: 1 + xy: y mol (x = 1, y = 0.1) (3) The solution of (1) and the solution of (2) are ultrasonically dissolved in 10 ml of ethanol by dissolving tetraorthosilicate (TEOS) in a 2-x molar ratio And the mixture was stirred to obtain a homogeneous composition.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

&Lt; Example 4-1 > K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.07 , Mn ²⁺ _0.03 Aluminum silicate phosphor

K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.07 Mn ²⁺ _0.03 (1) To 10 ml of water was added aluminum nitrate (Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ), europium chloride (EuCl ₃ ) and manganese chloride (MnCl ₂ ) at a ratio of 1 + x: 1 + x-0.07-0.03: 0.07: 0.03 mol respectively (x = 0) to obtain a solution. (2) To 10 ml of ethanol, (3) The solution of the above (1) and the solution of (2) are stirred by ultrasonics to obtain a homogeneous composition (2) by dissolving silicate (TEOS) To obtain a mixture.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 4-2 K _0.9 AlSi ₂ O ₈ : Ce ³⁺ _0.1 Aluminum silicate phosphor

_{K 0.9 AlSi 2 O 8: Ce} (1) for the preparation of a _0.1 ³⁺ phosphor of aluminum in water 10ml nitrate _{(Al (NO 3) 3)} , potassium nitrate (KNO _3), cerium nitrate (Ce (NO _{3) 3),} each 1 + x: 1 + x- 0.1: 0.1 mol ratio (to get the solution dissolved with x = 0), (2) tetra in ethanol 10ml ortho-silicate (TEOS) for 2-x mol ratio ( x was 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred by ultrasonic ultrasonic vibration to obtain a mixture having a uniform composition.

The mixture was thoroughly dried at 120 ° C until the solvent disappears and then heat-treated at a temperature of 1400 ° C for 3 hours in a reducing atmosphere of a mixed gas of 5% by volume of hydrogen and 95% by volume of nitrogen.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

&Lt; Test Example 6 >

K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.07 Mn ²⁺ _0.03 (Mn) prepared by using Eu (Eu) and Mn (Mn) as an activator in the above <Example 4-1> , An aluminum silicate fluorescent material having a composition of K _0.9 AlSi ₂ O ₈ : Ce ³⁺ _0.1 prepared by using cerium (Ce) as an activator in Example 4-2, The aluminum silicate phosphor of K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.1 composition prepared by using europium (Eu) as an activator was irradiated with ultraviolet light at a wavelength of 410 to 800 nm using a 450 nm filter under excitation of 395 nm wavelength, The change in the photoluminescence spectrum, which is the emission spectrum, was measured and the results are shown in Fig.

As shown in FIG. 7, K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.07 Mn ²⁺ _0.03 (C), K _0.9 AlSi ₂ O ₈ : Ce ³⁺ _0.1 prepared in Example 4-2 (B) prepared in Example 2-5 and K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.1 It was found that the composition of the aluminum silicate phosphor (A) exhibits different luminescence spectra depending on the activator.

Example 4-3 K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.07 , Mn ²⁺ _0.03 Aluminum silicate phosphor

K _0.9 AlSi ₂ O ₈ : Eu ²⁺ _0.07 Mn ²⁺ _0.03 (1) To 10 ml of water was added aluminum nitrate (Al (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ), europium chloride (EuCl ₃ ) and manganese chloride (MnCl ₂ ) at a ratio of 1 + x: 1 + x-0.07-0.03: 0.07: 0.03 mol respectively (x = 0) to obtain a solution. (2) To 10 ml of ethanol, (3) The solution of the above (1) and the solution of (2) are stirred by ultrasonics to obtain a homogeneous composition (2) by dissolving silicate (TEOS) To obtain a mixture.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

Example 4-4 K _0.9 AlSi ₂ O ₈ : Ce ³⁺ _0.1 Aluminum silicate phosphor

_{K 0.9 AlSi 2 O 8: Ce} (1) for the preparation of a _0.1 ³⁺ phosphor of aluminum in water 10ml nitrate _{(Al (NO 3) 3)} , potassium nitrate (KNO _3), cerium nitrate (Ce (NO _{3) 3),} each 1 + x: 1 + x- 0.1: 0.1 mol ratio (to get the solution dissolved with x = 0), (2) tetra in ethanol 10ml ortho-silicate (TEOS) for 2-x mol ratio ( x was 0) to obtain a solution. (3) The solution of (1) and the solution of (2) were stirred by ultrasonic ultrasonic vibration to obtain a mixture having a uniform composition.

The mixture was thoroughly dried at 120 &lt; [deg.] &Gt; C until the solvent was gone and heat treated at 1400 [deg.] C for 3 hours.

After the heat treatment, the mixture was cooled to 25 ° C and pulverized to a size of 10 ± 1 μm to prepare an aluminum silicate phosphor in powder form.

<Application Example 1>

Aluminum silicate-based phosphors of the composition M _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (M = K, x = 0, y = 0.1) The blue phosphor and the red phosphor were uniformly dispersed in an epoxy resin to prepare a hardened portion.

The light-emitting diode chip has a chip LED that emits photons in the ultraviolet wavelength region on a substrate made of Al ₂ O ₃ and adhered to the lead frame electrode (anode, cathode) with silver paste. Then, an aluminum silicate-based phosphor having a composition of M _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (M = K, x = 0, y = 0.1) The cured portion including the phosphor was applied and cured at 150 ° C for 1 hour to prepare a light emitting diode (LED).

The blue phosphor having an emission wavelength region of 420 nm to 480 nm was used and the red phosphor having an emission wavelength region of 570 nm to 750 nm was used.

&Lt; Test Example 7 >

The light emitting diode manufactured in <Application Example 1> was excited at an ultraviolet wavelength by driving at 3 V and 20 mA, and the emission intensity at a wavelength of 350 to 750 nm was measured. The results are shown in FIG.

8, the emission spectrum of the aluminum silicate-based phosphor having a composition of M _{1 + xy} Al _{1 + x} Si _{2 -x} O ₆ : Eu ²⁺ _y (M = K, x = 0, y = 0.1) , The emission spectrum of the blue phosphor and the emission spectrum of the red phosphor.

As described above, the present invention has been described with reference to the preferred embodiments, test examples and application examples of the present invention. However, it should be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as set forth in the following claims It will be understood that the invention may be variously modified and changed.

The phosphor represented by the following formula (1) of the present invention is an aluminum silicate-based phosphor excited by a wavelength of 250 to 500 nm represented by ultraviolet and blue light emitting diodes and having an emission wavelength spectrum in a range of 400 to 800 nm, Device, which is industrially applicable.

M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)

In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0? x? 1; y is 0 < y &lt; 0.5.

Claims (10)

An aluminum silicate-based phosphor represented by the following formula (1).
M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)
In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0.6? x? 1; y is 0 < y &lt; 0.5. The method according to claim 1,
Wherein the aluminum silicate-based phosphor represented by the formula (1) excites at a wavelength of 250 to 500 nm and exhibits luminescence characteristics at a wavelength of 400 to 800 nm. 3. The aluminum silicate-based phosphor according to claim 1 or 2, wherein x is 0.6 or 1, and y is 0.1. Adding aluminum (Al), silica (Si) and an alkali metal, an alkaline earth metal and an activator to a solvent, mixing and drying the mixture;
Heat treating the dry mixture;
And cooling the mixture to a room temperature and then pulverizing the phosphor to produce a phosphor represented by the following formula (1).
M _{1 + xy} Al _{1 + x} Si _2-x O ₆ : Q _y ????? (1)
In the above formula (1), M is any alkali metal selected from Li, Na, K, Rb and Cs; Q is at least one of Eu, Mn, Fe, Cr, Ca, Zn, Co, Ni, Y, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, At least one activator or a coactivator selected from the group consisting of tulium (Tm), ytterbium (Yb), lutetium (Lu), gallium (Ga), germanium (Ge) and indium (In); x is 0.6? x? 1; y is 0 < y &lt; 0.5. 5. The method of claim 4,
Wherein the aluminum (Al), the silica (Si), the alkali metal and the activator are at least one selected from oxides, chlorides, hydroxides, nitrates, carbonates and super oxides. The method according to claim 4 or 5,
Wherein x is 0.6 or 1, and y is 0.1. The method according to claim 6,
Wherein the aluminum silicate-based phosphor represented by the formula (1) excites at a wavelength of 250 to 500 nm and exhibits luminescence characteristics at a wavelength of 400 to 800 nm. A light emitting device comprising a phosphor represented by the formula (1) of claim 1. 9. The method of claim 8,
The light emitting element includes a light emitting element including the light emitting layer in which the phosphor is dispersed in epoxy delete

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