JP2010165996A - Led using visible-light excited phosphor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a useful light source which is soft for users and has an energy saving property as a surface light source capable of almost uniformly emitting light from the whole surface of a shell by: arranging visible-light excited/wavelength converting phosphors in the vicinity of the surface of a shell type LED to emit fluorescence on the surface of the shell type LED; and improving the directivity of a dot light source in LED illumination. <P>SOLUTION: The wavelength converting phosphor 103 is arranged in the vicinity of the surface of a shell lens of the shell type LED to uniformly emit fluorescence on the whole surface of the shell. The visible-light excited phosphor is arranged in the vicinity of the surface of the shell of the shell type LED, and a semiconductor light-emitting element in the shell type LED is arranged separately from the visible-light excited phosphor through the transparent resin of the shell. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a visible light excitation phosphor and an LED using the same.

  In a conventional LED, a light emitting surface of a monochromatic blue LED made of GaN is covered with a resin in which a phosphor such as YAG (yttrium, aluminum, garnet) is mixed with a silicone resin.

In order to produce a color tone close to a light bulb color using the YAG phosphor, a reddish component was mixed with YAG to produce a reddish color similar to a light bulb color.
However, since this reddish component is a dark phosphor, the luminance is hindered, resulting in a dark and dirty reddish. This is due to the absence of a bulb-colored phosphor with a beautiful reddish tint.
Of course, organic phosphors have beautiful reddish phosphors, but organic phosphors are degraded by strong light such as blue LEDs, so they cannot be used for wavelength conversion of blue LEDs.
If inorganic phosphors are used, they will not deteriorate even with strong light such as blue LEDs. However, most inorganic phosphors are ultraviolet-excited phosphors, and inorganic phosphors that can be excited by light in the visible region with a wavelength of 300 to 500 nm have been found. There wasn't.

The present invention provides means for solving this problem.
Provided is a phosphor that emits visible light when excited by light in the ultraviolet to visible region having a wavelength of ¥ 300 to 500 nm.

  In addition, the conventional bullet-type LED has a narrow directivity angle, emits extremely sharp directional light, shines directly under the LED, and emits intense light that hurts the eyes. The spread was scarce and this was one of the bottlenecks in LED lighting.

When resin-sealed flat LEDs are used, the directivity is somewhat improved, and some LEDs have a directivity angle of 50 degrees.
However, even under this flat LED, a strong light beam is emitted and cannot be seen directly.
In order to remedy this drawback, there is so-called indirect lighting that uses reflected light with the LED facing the ceiling, but the light attenuated due to reflection and suffered from insufficient illuminance.
There is also a method of diffusing the LED light by attaching a concave lens directly under the LED, but a strong luminous flux is still emitted on the central axis of the concave lens, and the dazzling defect cannot be improved.
There is also a method of attaching and diffusing a diffusion cone on an inverted cone directly under the LED, but there is a disadvantage that it is expensive.

On the other hand, the conventional filament incandescent bulb emits light at a solid angle of approximately 360 degrees, and emits light that is warm and soft.
For this reason, in Europe and the United States, there is a strong sense of resistance to LED lighting that emits sharp, cold light because it misses the light of old candles and lamps.

On the other hand, a conventional fluorescent lamp is a linear light source, but emits light with a spread.
However, the evaluation that the light of the fluorescent lamp is cold has been established, and there is also a light bulb color fluorescent tube, but it does not reach the color of the candle and the lamp.
For this reason, Westerners dislike fluorescent lamps and still use many halogen lamps that are incandescent lamps.
The display case of jewelry, perfume, and other products has poor color rendering properties of fluorescent lamps, so halogen lamps are still used. However, halogen lamps generate a lot of heat, and the temperature inside the display case rises, adversely affecting the products. is there.

There is a contradiction that the preference for a nostalgic candle and an incandescent light bulb close to a lamp goes against energy conservation.
The present invention provides a means to remedy this drawback. In other words, it provides a means to convert the cool color tone to the old color of candles and lamps using LEDs and wavelength conversion phosphors that can be lit with less power and have a lifetime that is five times that of fluorescent lamps.
In addition, the directivity of LEDs that are too sharp will be greatly improved to provide LEDs that emit soft, warm light that spreads close to incandescent bulbs.

The first problem to be solved is to improve the sharp directivity of the LED and to create a LED with a warm and wide directivity.
For this purpose, bullet-type LEDs are used. The material of the cannonball is usually made of epoxy or the like, and light generated from the semiconductor light emitting element is emitted instead of light having a sharp directivity due to the lens-shaped lens effect.
This is effective for buttons, signs and displays, LED signboards, etc., but not suitable for lighting.

  However, in the present invention, when a wavelength conversion phosphor is applied in the vicinity of the surface of the bullet lens, or the phosphor is disposed, the light generated from the semiconductor light emitting element in the bullet is repeatedly reflected in the bullet lens, and in the vicinity of the bullet surface. It has been found that since the arranged wavelength conversion phosphor is excited, the phosphor arranged on the surface of the shell can emit fluorescence almost uniformly.

As a means for arranging the wavelength conversion phosphor near the surface of the shell, there is a method of applying the wavelength conversion phosphor on the surface of the shell lens, but it is disadvantageous in that the operation cost is increased.
However, a resin is molded in the shape of a shell-type cap that covers the transparent lens of a shell-type LED (light-emitting diode), and a visible-light-excited phosphor is mixed into the resin of the shell-type cap, and a semiconductor light-emitting element inside the shell-type LED After passing through the transparent bullet-type lens, the light generated from the light enters the visible-light excitation phosphor in the bullet-type cap, and is wavelength-converted by the visible-light excitation phosphor, and a part of it is outside the bullet-type cap. The remainder of the light emitted and incident on the visible-light-excited phosphor is reflected by the visible-light-excited phosphor, returns to the transparent shell-type lens, and then enters the other part of the shell-type cap, and part of it is bullet-type It was discovered that the visible light-excited phosphor in the shell-shaped cap shines almost evenly by being discharged outside the cap and the remainder re-entering into the transparent shell-shaped lens again.

In addition, a method of forming a resin cap so as to cover the shell and mixing the wavelength conversion phosphor into the resin when manufacturing the resin cap is lower in cost.
This bullet-type cap can be put on a conventional bullet-type LED, but if there is an air gap between the surface of the bullet-type LED and the bullet-type resin cap, the light excitation efficiency will decrease and light emission will spread well It was found that there are cases where cannot be obtained.
Specifically, a visible light excitation phosphor is mixed in a resin, the resin is molded in the shape of a shell-shaped cap, a gel-like transparent resin is filled in the cap recess, and the light emitting surface of the resin-sealed flat LED is formed. After covering the cap so as to cover, the gel-like transparent resin is cured, and light generated from the light emitting surface of the resin-sealed flat LED passes through the cured gel-like transparent resin and the bullet-shaped cap Is incident on the visible-light-excited phosphor, wavelength-converted by the visible-light-excited phosphor, part of which is emitted to the outside of the shell-type cap, and the rest of the light incident on the visible-light-excited phosphor is reflected by the visible-light-excited phosphor. After returning into the gel-like transparent resin, it enters the other part of the shell-shaped cap, a part of which is released to the outside of the shell-shaped cap, and the remaining part returns again into the gel-like transparent resin. Repeat Now glowing substantially equally visible light excitation phosphor in bullet type cap by, bullet type LED has been found that can be manufactured at the lowest cost.
In addition, since the wavelength conversion phosphor is mixed in advance in the resin of the resin cap placed on the surface of the shell, the wavelength conversion phosphor is disposed in the vicinity of the surface of the shell lens of the shell type LED.

When a resin plate mixed with visible light-excited phosphor is placed on the surface of the transparent resin on the light emitting surface of the flat LED sealed with a transparent resin, the light generated from the semiconductor light emitting element inside the flat LED is After passing through the transparent resin, it is incident on the resin plate mixed with the visible light excited phosphor, converted in wavelength by the visible light excited phosphor, and a part thereof is outside the resin plate mixed with the visible light excited phosphor. The remainder of the light emitted and incident on the resin plate mixed with the visible light-excited phosphor is reflected by the visible light-excited phosphor, returns to the transparent resin, and then another resin plate mixed with the visible-light-excited phosphor. Part of the light is incident on the part and released to the outside of the resin plate mixed with the visible light-excited phosphor, and the remaining part returns to the transparent resin again. By repeating this, the inside of the resin plate mixed with the visible-light-excited phosphor The visible light excitation phosphor can be made to shine almost evenly

The present invention also provides means for solving the second problem, that is, the problem that the light of the conventional fluorescent lamp is too cold.
A solution to this problem is provided by a wavelength converting phosphor placed on the surface of the LED.
Many of the conventional inorganic wavelength conversion phosphors are ultraviolet-excited wavelength conversion phosphors.
For example, an inorganic phosphor applied on the inner surface of a fluorescent tube is excited by ultraviolet rays inside the fluorescent tube to emit visible light.
For this reason, UV-excited phosphors for fluorescent tubes have been well studied, and many UV-excited phosphors have been put into practical use.

However, since there has been little demand for phosphors excited with visible light of 300 nm to 500 nm, there has been little research and no effective visible light excitation phosphors have been found.
In view of this point, the inventor's group conducted research on visible light excitation phosphors, and found inorganic phosphors that were effectively excited with visible light and that did not deteriorate even with strong light of a monochromatic blue LED. Their molecular formulas are listed in (1) to (10) of claim 5.
The visible light excitation phosphor shown in (1) of claim 5 and the following (1) converts light from a blue-white or blue LED into an orange light bulb color.
Further, the visible light excitation phosphor shown in (1) of claim 5 and the following (1) has a molecular formula different from that of conventionally known strontium silicate (Non-patent Document 1).
Moreover, the visible light excitation fluorescent substance shown to (2) of Claim 5, and the following (2) converts the light from blue-white or blue LED into white.

The visible light excitation phosphor used in the present invention is
(1) An orange phosphor that emits light when excited with light in the ultraviolet to visible region having a wavelength of 200 to 500 nm, and has a general formula;
_{(Sr 1 - x Eu x)} 3 SiO 5 ( where, 0 <x ≦ 0.10)
An orange phosphor that is composed of a single-phase crystal and is excited by visible light from the near ultraviolet of 200 to 500 nm and emits light at a peak emission wavelength of 580 to 600 nm.

(2) Chemical composition formula shown in Formula 1 including silicate and activator:
a M O · b M 'O · c S i O 2 · d R: E u x · L n y
(Equation 1)
In Formula 1, M is one or more elements selected from S r, C a, B a, and Z n;
M ′ is one or more elements selected from M g, C d, and B e;
R is one or two components selected from B ₂ O ₃ and P ₂ O ₅ ;
L n is N d, D y, H o, T m, L a
, One or more elements selected from P r, T b, C e and S b;
a, b, c, d, x, and y are number of moles, 0.
6 ≦ a ≦ 6,
0 ≦ b ≦ 5, 1 ≦ c ≦ 9, 0 ≦ d
≦ 0. 7, 0. 0 0 0 0 1 ≤ x ≤ 0. 2, 0 <y ≦ 0. 3)
Excited with visible light from 2 5 0 to 5 0 0 nm in the near ultraviolet, 4
The emission spectrum of 2 0 to 6 5 0 nm is emitted, the peak value is 4 5 0 to 5 8 0 nm, and the emission of blue, blue green, green, green yellow or yellow afterglow appears. A feature of long afterglow phosphor.

(3) M 1 in the formula 1 is one or two elements selected from S r and C a;
M ′ is M g; L n is one or two elements selected from N d, D y and H o; 6 ≦ a ≦ 4, 0. 6
≦ b ≦ 4, 1 ≦ c ≦ 5, 0 ≦ d ≦ 0. 4. The long afterglow phosphor according to (2) above, wherein R 1 is one or a variety of components selected from B ₂ O ₃ and P ₂ O ₅ .

(4) In the above formula 1, 0 of the element in M 1 and / or M ′
The long afterglow fluorescence according to (2) above, wherein 40% mol is replaced by one or more elements selected from Ba, Zn, Cd and Be. body.

(5) In the above formula 1, the chemical composition formula _{M 2 M g S i 2 O} 7: E u x, L n y or _{M 3 M g S i 2 O} 8: E u x, a L n y, 0. 0 0 0 0 1 ≤ x ≤ 0. 2, 0 <y ≤ 0
. 3 and M are S r 1 -z C az (0 ≦ z ≦ 1), and L n is N d, D y, Ho, T m, La, P
The long afterglow phosphor as described in (2) above, which is one or many kinds of components selected from r 1, T b, C e and S b.

(6) In the above formula 1, the chemical composition formula is B a ₅ Si ₈ O _{2 1} d R: E ux, D y y, and R 1 is selected from B ₂ O ₃ , P ₂ O ₅ One or two components, d 1, x 2 and y 3 represent the number of moles,
0 <d ≦ 0. 7, 0. 0 0 0 0 1
≤ x ≤ 0. 2,
0 <y ≦ 0. 3. The long afterglow phosphor according to (2) above, wherein

(7) A S n _{O 3} or _{A n + 1 S n n O} 3 n + 1
(Where A is 1 selected from the group consisting of M g, C a, S r and B a.
Or, 2 or more alkaline earth metal elements are represented, and n = 1 or 2. )
A rare earth element and / or a base material composed of an alkaline earth metal and an oxide of Sn.
Alternatively, an inorganic oxide phosphor to which a transition metal element is added, and the rare earth elements are L a, C e, P r, S m, E u, G d, T b, D y, E r and T m.
An inorganic oxide phosphor that is one or more elements selected from the group consisting of: Sr ₃ Sn ₂ O ₇ : S m phosphor when the excitation wavelength is 2 5 4 nm The wavelength shows four peaks, about 5 7 0, 5 8 0, 6 1 0, 6 2 0 nm, and its appearance is orange light emission,
Or, the emission wavelength of the Sr ₂ Sn O ₄ : T i phosphor is blue emission having a peak at about 4 10 nm,
The phosphor characterized in that the emission wavelength of the C a S nO ₃ : P r phosphor is white to yellow emission having a peak at about 4 80 nm.


(8) The rare earth element addition amount is 0. The inorganic oxide phosphor according to (7), wherein the content is 0 2 to 10 mol%.

(9) The amount of transition metal element added is 0. 5 to 15 m
The inorganic oxide phosphor according to (7), which is ol%.

(10) The inorganic oxide phosphor according to (7), wherein both rare earth element E u and transition metal element Ti are added.

Each of these inorganic phosphors is produced by a group company managed by the present applicant, and can be immediately put into practical use.
The manufacturing method is to mix powders of oxides and carbonates of each metal element, press and sinter, re-pulverize, press and sinter and re-pulverize repeatedly to make inorganic phosphor powder. A known solid phase method for producing can be used.

The experiment was conducted by arranging the wavelength converting phosphor as described above in the vicinity of the surface of the bullet lens of the bullet type LED.
The wavelength-converting phosphor shown in (1) of claim 5 was applied to the surface of a 1 W bullet-type LED bullet lens 10 mmΦ to a thickness of 100 microns and used for the experiment.
Record the results.
The above-mentioned 1 W bullet-type LED 10 mmΦ × 3 pieces were attached to a rail-like heat sink, and the entire light emitting part length was 110 mm to form a 10 mm width LED lighting, and each LED was caused to emit light by flowing a current of 300 mA.
The power consumption of the three LEDs was 2.643W. When an illuminance meter was placed 1 m directly below the LED illumination and the illuminance was measured, it was 14.52 Lux.

On the other hand, when the illuminance meter was placed 1 m directly below a 4 W fluorescent tube with a light emitting part length of 110 mm and a tube diameter of 15 mm, and the illuminance was measured, it was 1.98 Lux.

Therefore, when calculating the illuminance per 1W of the three LEDs with the same light emitting area and the fluorescent lamp, the fluorescent lamp is 0.496 Lux per 1W, while the LED lighting is 5.49 Lux per 1W, and the wavelength conversion It was found that the illuminance per 1 W of the LED lighting was actually 11.09 times the illuminance per 1 W of the fluorescent lamp.
This is evidence of how effective the visible light excitation / wavelength conversion phosphor of the present invention is.
The three wavelength conversion LEDs are not only brighter than 4W fluorescent lamps, but also emit warm colors like a small incandescent bulb and light that spreads like a bulb, as if three small bulbs were lined up. A lighting effect was obtained.
This indicates that the light spreading of the LED of the present invention is very close to the light spreading of a conventional incandescent bulb, and the color is similar to that of an incandescent bulb.

In order to carry out the present invention, a transparent liquid resin having no wavelength conversion function such as a transparent silicone resin is cast on the concave surface portion of the shell-shaped resin cap, and the transparent resin is covered so as to cover the light emitting surface of the flat LED. Curing can produce bullet-type LEDs at the lowest cost.
In addition, since the wavelength conversion phosphor is mixed in advance in the resin of the resin cap placed on the surface of the shell, the wavelength conversion phosphor is disposed in the vicinity of the surface of the shell lens of the shell type LED.

The best mode embodiment 1 is shown in FIG. In FIG. 1, a bullet-type resin cap 105 is placed so as to cover the light-emitting surface 102 of the resin-sealed flat LED 101. The concave portion of the shell-shaped resin cap 105 is filled with a transparent gel 104 of transparent silicone resin, and the transparent gel 104 is cured by placing the transparent gel 104 so as to cover the light emitting surface 102 of the flat LED 101.
In this way, the light generated from the light emitting surface 102 of the resin-sealed flat LED 101 passes through the cured transparent gel 104 and enters the wavelength conversion phosphor 103 disposed in the vicinity of the surface of the cannonball 105, A part is transmitted and emitted to the outside of the cannonball 105, a part is reflected by the wavelength conversion phosphor 103, returns to the inside of the transparent gel 104, is repeatedly reflected inside the cannonball 105, and is arranged near the surface of the cannonball 105. The wavelength-converting phosphor 103 is illuminated uniformly.
As a result, the shell 105 emits soft light that spreads like an incandescent bulb.

  As another embodiment, as shown in FIG. 2, a resin cap 202 covering the conventional bullet-type LED shell 201 can be formed, and the wavelength conversion phosphor 203 can be mixed into the resin of the resin cap 202. Reference numeral 204 denotes a resin for a conventional lens of the conventional LED 201. The LED chip is shown at 205.

As another embodiment, a bullet-type LED 302 can be housed inside a transparent resin tube 301 as shown in FIG. Reference numeral 303 indicates the surface of the transparent resin injected into the gap between the tube 301 and the bullet-type LED 302. The transparent resin 303 is injected between the bullet-type LED 302 and the cylinder 301, and the wavelength conversion phosphor 304 is mixed inside the transparent resin 303. Even in this case, substantially the same effect as in Example 1 was obtained.

Further, the embodiment shown in FIG. 4 shows a resin-sealed flat LED. The GaN light emitting surface of the monochromatic blue LED semiconductor light emitting element 401 is covered with a transparent plastic body 402 having no wavelength conversion function and sealed with resin. Then, a resin plate 403 is covered so as to cover the transparent plastic body 402 having no wavelength conversion function. If the wavelength conversion phosphor 404 is mixed inside the resin plate 403, the light emitted from the resin-sealed flat LED enters the wavelength conversion phosphor 404, is wavelength-converted, and is emitted to the outside of the resin plate 403. Flat type LED is obtained.
The light generated from the light emitting surface of the single-color blue LED semiconductor light-emitting element made of GaN, either this flat LED or the bullet-type LED of the previous embodiment, once passed through the transparent plastic plate and then mixed with the wavelength conversion phosphor. It is the same in that it is incident on the resin plate.
That is, in both cases, the single-color blue LED semiconductor light-emitting element made of GaN and the resin plate mixed with the wavelength conversion phosphor are separated by a transparent plastic body having no wavelength conversion function and are not in direct contact with each other.
In the fourth embodiment, the light generated from the monochromatic blue LED is once radiated into the transparent plastic body 402 having no wavelength conversion function, and a light pool is formed in the transparent plastic body 402 having no wavelength conversion function, and then wavelength-converted fluorescence. Incident on the body 404. Therefore, the light incident on the wavelength conversion phosphor 404 excites the wavelength conversion phosphor 404 and then radiates to the outside of the resin plate 403 mixed with the component reflected and reflected by the wavelength conversion phosphor 404 and the wavelength conversion phosphor 404. The wavelength-converting phosphor in the resin plate 403 is evenly lit.

Further, in claim 1 to claim 4, the LED semiconductor light-emitting element inside the bullet-type LED or the resin-encapsulated flat LED is a blue-white LED bare chip, and the blue-white LED bare chip structure is a GaN single-color blue LED bare chip. It is characterized by being a blue-white LED bare chip covered with a wavelength conversion phosphor such as YAG, a bullet-type lens or a resin-sealed flat type LED on the blue-white LED bare chip, a resin plate, The LED according to any one of claims 1 to 4, wherein the wavelength conversion phosphor shown in claim 5 is arranged in the vicinity of the surface of the bullet-type lens or in a resin plate that covers a resin-sealed flat LED. When made, the brightness was the greatest.
The reason for this is that the blue-white LED has already been covered with a white wavelength conversion phosphor such as YAG on the bare chip, so it emits strong white light in addition to blue, thus increasing the brightness. -ing

As Comparative Example 1, illuminance when a GaN single-color blue LED is used instead of the blue-white LED shown in Example 5 and a resin plate is arranged on the light emitting surface of the single-color blue LED, and a wavelength conversion phosphor is mixed in the resin plate. Was lower than the illuminance of the LEDs of the other examples.
The reason for this is that if the wavelength is not converted by masking the strong blue color of a GaN single-color blue LED, it will not be close to white, so the amount of wavelength-converting phosphor must be used much more than in the previous example, so the illuminance is low. It has declined.
In this way, a bullet-type LED or resin-sealed flat LED is made using only a GaN single-color blue LED that does not cover any wavelength-converting phosphor, and it is placed near the surface of the bullet lens or on a resin-sealed flat LED. When the wavelength conversion phosphor shown in claim 5 is arranged in the resin plate, the brightness is reduced as compared with the case where the blue-white LED is used.

In addition, when the wavelength conversion phosphor 502 is mixed in the entire resin of the cannonball 501 as Comparative Example 2 as shown in FIG. 5, the regressive reflection as in Examples 1 to 5 hardly occurs, soft light with less directivity, and a certain amount of light. Strong illuminance is not obtained together.
This is because each wavelength-converting phosphor particle dispersed in the whole shell 501 absorbs and diffuses light and weakens illuminance. Reference numeral 503 denotes a semiconductor light emitting element.

FIG. 6 is a cross-sectional view illustrating Example 1 shown in FIG. 1, and arrows indicate light generated from the semiconductor light emitting element 101. Light enters the wavelength conversion phosphor 103 as indicated by the arrow and is reflected back.
FIG. 7 shows a spectrum of light generated from a bullet-type LED when the visible light excitation / wavelength conversion phosphor 103 shown in (1) of claim 5 is arranged on the surface of a 1 W blue-white bullet-type LED.

Moreover, the following was searched as prior art of this invention. However, the present invention does not conflict with any of them.
In Patent Document 1 below, an LED bare chip using only a GaN single color blue LED is covered with a wavelength conversion phosphor such as YAG, and the wavelength conversion fluorescence such as YAG is applied to the bare chip of GaN single color blue LED as in the present invention. This is different from a configuration in which a light-emitting surface of an LED covered with a body is covered with a transparent plastic body that does not have a wavelength conversion function and a resin in which a wavelength conversion phosphor is disposed on the outer side.
Patent No. 2900928 Patent No. 2927279 Patent No. 3503139 Patent No. 3700502 Patent No. 3724490 Patent No. 3724498 JP 2008-160140 LIGHT EMITTING DEVICE AND DISPLAY DEVICE JP 2006-332692 LIGHT EMITTING DEVICE JP 2006-041096 LIGHT EMITTING DEVICE AND PHOSPHOR JP 2005-317985 LIGHT EMITTING DEVICE AND DISPLAY DEVICE JP 20052005311 Alkaline earth metal borate fluorescence Body and light-emitting device using the same JP-A-2005-232305 Alkaline earth metal aluminate phosphor and light-emitting device using the same JP-A-2005-146172 Light-emitting device and phosphor for light-emitting device JP 2003-179259 Display device JP 2002-335010 Nitride semiconductor light emitting device JP 2002-198573 LED Light emitting diode JP 2000-208815 Light emitting diode JP 11-261114 Light emitting diode JP 11-243232 LED display JP 10-242513 LIGHT EMITTING DIODE AND DISPLAY DEVICE USING THE SAME 98/005078 LIGHT EMITTING DEVICE AND DISPLAY DEVICE From “LED Reliability Handbook” P.66; “The conventional silicate phosphor is Sr2SiO4; Eu” (published by Nikkan Kogyo Shimbun) Nichia, Toyoda Gosei, Citizen Electronics, Asahi Rubber, OSRAM, It is recommended to implement the present invention using blue and white LEDs manufactured by Lumileds.

Since the present invention is configured as described above, it is possible to provide a new LED illumination that converts the cold light of a conventional fluorescent lamp into warm light.
In addition to that, it can improve the sharp directivity of conventional LEDs and provide LED lighting that is as soft and omnidirectional as an incandescent bulb. For this reason, it is possible to provide LED lighting that replaces incandescent light bulbs that consume too much energy, and illumination that is omnidirectionally spread like incandescent light bulbs. A fluorescent lamp consumes about one-fifth of the power consumption of an incandescent lamp with the same brightness, and conventional LED lighting consumes half of the power consumption of a fluorescent lamp.
However, the power consumption of the bullet-type LED with the wavelength-converting phosphor of the present invention is even less than the power consumption of the conventional LED lighting, so the use of LED lighting with the wavelength-converting phosphor of the present invention reduces carbon dioxide emissions. It can contribute greatly.

As described above, the present invention has two great effects of eye-friendly illumination and energy saving, and is extremely useful in industry.
The present invention is configured as described above, and since all the means can be realized by using known means, it is obvious that the structure of the present invention is completed.
Further, the present invention is not limited to the above-described embodiments, the text, and the claims by the principle of equality, and it goes without saying that various modifications and derived examples are possible.

Sectional drawing which shows the Example which mixed the wavelength conversion fluorescent substance beforehand in resin of the resin cap covered on the surface of the conventional bullet-type LED. Sectional drawing which shows the Example which made the resin cap which covers the bullet of a bullet-type LED, and mixed the wavelength conversion fluorescent substance in resin of this resin cap. Sectional drawing which shows the Example which accommodated the bullet-type LED inside the cylinder of transparent resin. Sectional drawing which shows the Example which attached the transparent plastic board to the light emission surface of resin-sealed flat type LED, and has arrange | positioned the resin board which mixed the wavelength conversion fluorescent substance so that this transparent plastic board may be covered. Sectional drawing which shows the comparative example which mixed wavelength conversion fluorescent substance into resin of the bullet type LED itself. 1 is a cross-sectional view illustrating Example 1 illustrated in FIG. 1, and arrows indicate light generated from the semiconductor light emitting element 101. Light enters the wavelength conversion phosphor 103 as indicated by the arrow and is reflected back. FIG. 5 is a spectrum of light generated from a bullet-type LED when the visible light excitation / wavelength-converting phosphor 103 shown in (1) of claim 5 is arranged on the surface of a 1 W blue-white bullet-type LED.

101; resin-encapsulated flat LED chip 102; light emitting surface 103 of a flat semiconductor light emitting device; wavelength conversion phosphor 104 mixed in a shell-shaped resin cap; transparent resin 105 filled in a shell-shaped cap ; Shell-shaped resin cap

201: Conventional bullet-type LED
202; Resin cap 203 over the lens of a conventional bullet-type LED; Wavelength conversion phosphor 204 mixed in the resin cap; Resin 205 of a bullet-type lens; Semiconductor light emitting device

301; transparent resin cylinder 302; conventional bullet-type LED shell-type lens 303; cast transparent resin surface 304; wavelength-converting phosphor 305 mixed in the cast transparent resin; semiconductor light-emitting element

401: Conventional resin-sealed flat LED semiconductor light emitting element 402; Transparent plastic body 403 having no wavelength conversion function; Resin plate 404 covering the light emitting surface; Wavelength converting phosphor mixed with the resin plate covering the light emitting surface

501; conventional bullet-type LED bullet-type lens 502; wavelength-converting phosphor 503 mixed in the resin of the bullet-type lens; semiconductor light-emitting element

Claims (6)

  Resin is molded in the shape of a shell-type cap that covers the transparent lens of a shell-type LED (light-emitting diode), and a visible-light-excited phosphor is mixed into the resin of the shell-type cap. The generated light passes through the transparent bullet-type lens and then enters the visible-light-excited phosphor inside the bullet-type cap. The wavelength is converted by the visible-light-excited phosphor, and a part of the light is emitted to the outside of the bullet-type cap. The remainder of the light incident on the visible light excitation phosphor is reflected by the visible light excitation phosphor, returns to the transparent bullet-type lens, and then enters the other part of the bullet-type cap, and a part of the bullet-type cap The LED is characterized in that the visible light-excited phosphor in the shell-shaped cap shines almost uniformly by repeating this process and returning to the transparent shell-shaped lens. Visible light excitation phosphor is mixed with resin, the resin is molded in the shape of a shell-shaped cap, the cap recess is filled with a gel-like transparent resin, and the light emitting surface of the resin-sealed flat LED is covered. After covering the cap, the gel-like transparent resin is cured, and light generated from the light emitting surface of the resin-sealed flat LED passes through the cured gel-like transparent resin to excite visible light in the shell-shaped cap. It is incident on the phosphor, wavelength-converted by the visible light excitation phosphor, part of which is emitted to the outside of the shell-shaped cap, and the remainder of the light incident on the visible light excitation phosphor is reflected by the visible light excitation phosphor. After returning to the transparent resin, it enters the other part of the shell-shaped cap, part of it is released to the outside of the shell-shaped cap, and the remaining part returns to the gel-like transparent resin again, and this is repeated. Gun LED, wherein a visible light excitation phosphor in the mold cap has to shine substantially equal.   An LED comprising: a visible light-excited phosphor disposed near the surface of a shell-type LED shell, and the semiconductor light-emitting element in the shell-type LED and the visible-light-excited phosphor are separated from each other via a shell transparent resin.   A resin plate mixed with visible light-excited phosphor is placed on the surface of the transparent resin on the light emitting surface of the flat LED sealed with a transparent resin, and the light generated from the semiconductor light emitting element inside the flat LED is transparent. After passing through the resin, it enters the resin plate mixed with the visible light-excited phosphor, is wavelength-converted by the visible light-excited phosphor, and part of it is emitted outside the resin plate mixed with the visible-light excited phosphor. The remaining part of the light incident on the resin plate mixed with the visible light excitation phosphor is reflected by the visible light excitation phosphor and returns to the transparent resin, and then another part of the resin plate mixed with the visible light excitation phosphor. A part of which is emitted to the outside of the resin plate mixed with the visible light-excited phosphor, and the remaining part returns to the transparent resin again. By repeating this, the inside of the resin plate mixed with the visible-light-excited phosphor is repeated. The visible light excitation phosphor is designed to emit light almost uniformly. LED that. The LED according to any one of claims 1 to 4, wherein the visible light excitation phosphor is any one of the following (1) to (10).

(1) An orange phosphor that emits light when excited with light in the ultraviolet to visible region having a wavelength of 200 to 500 nm, and has a general formula;
_{(Sr 1 - x Eu x)} 3 SiO 5 ( where, 0 <x ≦ 0.10)
An orange phosphor characterized in that it is composed of single-phase crystals.

(2) Chemical composition formula shown in Formula 1 including silicate and activator:
a M O · b M 'O · c S i O 2 · d R: E u x · L n y
(Equation 1)
In Formula 1, M is one or more elements selected from S r, C a, B a, and Z n;
M ′ is one or more elements selected from M g, C d, and B e;
R is one or two components selected from B ₂ O ₃ and P ₂ O ₅ ;
L n is N d, D y, H o, T m, L a
, One or more elements selected from P r, T b, C e and S b;
a, b, c, d, x, and y are number of moles, 0.
6 ≦ a ≦ 6,
0 ≦ b ≦ 5, 1 ≦ c ≦ 9, 0 ≦ d
≦ 0. 7, 0. 0 0 0 0 1 ≤ x ≤ 0. 2, 0 <y ≦ 0. 3)
Under the excitation of short wave light of 2 5 0 to 5 0 0 nm, 4
The emission spectrum of 2 0 to 6 5 0 nm is emitted, the peak value is 4 5 0 to 5 8 0 nm, and the emission of blue, blue green, green, green yellow or yellow long afterglow appears. A feature of long afterglow phosphor.

(3) M 1 in the formula 1 is one or two elements selected from S r and C a;
M ′ is M g; L n is one or two elements selected from N d, D y and H o; 6 ≦ a ≦ 4, 0. 6
≦ b ≦ 4, 1 ≦ c ≦ 5, 0 ≦ d ≦ 0. 4. The long afterglow phosphor according to (2) above, wherein R 1 is one or a variety of components selected from B ₂ O ₃ and P ₂ O ₅ .

(4) In the above formula 1, 0 of the element in M 1 and / or M ′
The long afterglow fluorescence according to (2) above, wherein 40% mol is replaced by one or more elements selected from Ba, Zn, Cd and Be. body.

(5) In the above formula 1, the chemical composition formula _{M 2 M g S i 2 O} 7: E u x, L n y or _{M 3 M g S i 2 O} 8: E u x, a L n y, 0. 0 0 0 0 1 ≤ x ≤ 0. 2, 0 <y ≤ 0
. 3 and M are S r 1 -z C az (0 ≦ z ≦ 1), and L n is N d, D y, Ho, T m, La, P
The long afterglow phosphor as described in (2) above, which is one or many kinds of components selected from r 1, T b, C e and S b.

(6) In the above formula 1, the chemical composition formula is B a ₅ Si ₈ O _{2 1} d R: E ux, D y y, and R 1 is selected from B ₂ O ₃ , P ₂ O ₅ One or two components, d 1, x 2 and y 3 represent the number of moles,
0 <d ≦ 0. 7, 0. 0 0 0 0 1
≤ x ≤ 0. 2,
0 <y ≦ 0. 3. The long afterglow phosphor according to (2) above, wherein

(7) A S n _{O 3} or _{A n + 1 S n n O} 3 n + 1
(Where A is 1 selected from the group consisting of M g, C a, S r and B a.
Or, 2 or more alkaline earth metal elements are represented, and n = 1 or 2. )
A rare earth element and / or a base material composed of an alkaline earth metal and an oxide of Sn.
Alternatively, an inorganic oxide phosphor to which a transition metal element is added, and the rare earth elements are L a, C e, P r, S m, E u, G d, T b, D y, E r and T m.
An inorganic oxide phosphor that is one or more elements selected from the group consisting of:

(8) The rare earth element addition amount is 0. The inorganic oxide phosphor according to (7), wherein the content is 0 2 to 10 mol%.

(9) The amount of transition metal element added is 0. 5 to 15 m
The inorganic oxide phosphor according to (7), which is ol%.

(10) The inorganic oxide phosphor according to (7), wherein both rare earth element E u and transition metal element Ti are added.   5. The semiconductor light-emitting element inside a flat LED sealed with a bullet-type LED or a transparent resin is a blue-white LED semiconductor light-emitting element, and the blue-white LED semiconductor light-emitting element has a monochromatic structure of GaN. It is a blue-white LED semiconductor light-emitting element in which a light-emitting surface of a blue LED semiconductor light-emitting element is covered with a wavelength conversion phosphor such as YAG, and a bullet-type lens or resin is provided on the light-emitting surface of the blue-white LED semiconductor light-emitting element. The LED according to any one of claims 1 to 4, wherein a plate is disposed, and the wavelength conversion phosphor shown in claim 5 is disposed in the vicinity of the surface of the bullet-type lens or in a resin plate.

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