Title: Light-emitting device
Abstract: A light-release side of a light-emitting element having a main emission peak wavelength in a wavelength range of not longer than 500 nm is covered with a sealing resin containing organic fluorescent substance-containing silicone as an additive.
Patent Number: 6,841,933 Issued on 01/11/2005 to Yamanaka, et al.
| Inventors:
|
Yamanaka; Osamu (Aichi, JP);
Nawashiro; Mitsuhiro (Aichi, JP)
|
| Assignee:
|
Toyoda Gosei Co., Ltd. (Aichi, JP)
|
| Appl. No.:
|
171527 |
| Filed:
|
June 14, 2002 |
Foreign Application Priority Data
| Jun 15, 2001[JP] | P2001-182543 |
| Current U.S. Class: |
313/512; 257/89; 428/403 |
| Intern'l Class: |
H01J 001/62; H01L033/00 |
| Field of Search: |
313/512,498,501,504,483
257/100,89,791,160,99
428/403
|
References Cited [Referenced By]
U.S. Patent Documents
| 5220243 | Jun., 1993 | Klinedinst et al. | 313/502.
|
| 5753381 | May., 1998 | Feldman et al. | 428/696.
|
| 5847507 | Dec., 1998 | Butterworth et al. | 313/512.
|
| 5856009 | Jan., 1999 | Nishio et al. | 428/404.
|
| 5910333 | Jun., 1999 | Lin et al. | 427/69.
|
| 5958591 | Sep., 1999 | Budd | 428/403.
|
| 5959316 | Sep., 1999 | Lowery | 257/98.
|
| 6011352 | Jan., 2000 | Haynes | 313/505.
|
| 6069440 | May., 2000 | Shimizu et al.
| |
| 6084250 | Jul., 2000 | Justel et al. | 257/89.
|
| 6245259 | Jun., 2001 | Hohn et al. | 252/301.
|
| 6252254 | Jun., 2001 | Soules et al. | 257/89.
|
| 6255670 | Jul., 2001 | Srivastava et al. | 257/89.
|
| 6294800 | Sep., 2001 | Duggal et al. | 257/89.
|
| 6310364 | Oct., 2001 | Uemura | 257/100.
|
| 6351069 | Feb., 2002 | Lowery et al. | 313/512.
|
| 6396082 | May., 2002 | Fukasawa et al. | 257/79.
|
| 6447908 | Sep., 2002 | Yun et al. | 428/403.
|
| 6456002 | Sep., 2002 | Klinedinst et al. | 313/503.
|
| 6513949 | Feb., 2003 | Marshall et al. | 362/231.
|
| 6552368 | Apr., 2003 | Tamai et al. | 257/98.
|
| 2002/0043926 | Apr., 2002 | Takahashi et al.
| |
| Foreign Patent Documents |
| 2000-208818 | Jul., 2000 | JP.
| |
Primary Examiner: Williams; Joseph
Assistant Examiner: Dong; Dalei
Attorney, Agent or Firm: McGinn & Gibb, PLLC
Claims
What is claimed is:
1. A light-emitting device, comprising:
a light-emitting element;
a first sealing member that covers a light release side of said
light-emitting element; and
a plurality of silicone members that include at least one organic
fluorescent substance, said plurality of silicone members being scattered
within said first sealing member.
2. A light-emitting device according to claim 1, wherein a main emission
peak wavelength of said light-emitting element comprises a wavelength
range of from 360 nm to 400 nm.
3. A light-emitting device according to claim 1, wherein said
light-emitting element comprises a Group III nitride compound
semiconductor light-emitting element.
4. A light-emitting device according to claim 1, wherein each of said
plurality of silicone members comprises a ball-like shape.
5. A light-emitting device according to claim 4, wherein said each of said
plurality of silicone members comprises a diameter in a range of from 1 um
to 50 um.
6. A light-emitting device according to claim 1, wherein said plurality of
silicone members comprises a silicone resin impregnated with said at least
one organic fluorescent substance.
7. A light-emitting device according to claim 1, wherein said plurality of
silicone members is localized on a light-emitting element side of said
first sealing member.
8. A light-emitting device according to claim 1, wherein said at least one
organic fluorescent substance comprises a plurality of organic fluorescent
substances.
9. A light-emitting device according to claim 1, wherein said plurality of
silicone members comprises a plurality of first silicone members, which
include a first organic fluorescent substance, and a plurality of second
silicone members, which include a second organic fluorescent substance.
10. A light-emitting device according to claim 1, wherein said first
sealing member comprises an epoxy resin.
11. A light-emitting device according to claim 1, further comprising at
least one inorganic fluorescent substance scattered within said sealing
member.
12. A light-emitting device according to claim 11, wherein said inorganic
fluorescent substance comprises a green fluorescent substance.
13. A light-emitting device according to claim 1, further comprising a
second sealing member that covers said first sealing member.
14. A light-emitting device according to claim 1, wherein a main emission
peak wavelength of said light-emitting element is not longer than 500 nm.
15. A light-emitting device according to claim 1, further comprising:
a layer disposed between said light-emitting element and said first sealing
member, said layer comprising a substance different from that of said
first sealing member.
16. A light-emitting device according to claim 1, wherein said plurality of
silicone members is scattered within a part of said first sealing member.
17. A light-emitting device according to claim 1, wherein said first
sealing member comprises a laminated structure including a first layer,
which includes a first concentration of said plurality of silicone
members, and a second layer, which includes a second concentration of said
plurality of silicone members.
18. A light-emitting device according to claim 1, wherein said second
sealing member includes at least one fluorescent substance.
19. A light-emitting device according to claim 1, wherein said
light-emitting element is disposed within a cup-like portion, which
reflects light emitted from said light-emitting element toward said light
release side.
20. A light-emitting device according to claim 19, wherein a bottom of said
cup-like portion comprises an electrode.
21. A light-emitting device, comprising:
a light-emitting element;
a sealing member formed on said light-emitting element; and
a plurality of silicone members which comprise at least one organic
fluorescent substance, formed in said sealing member.
22. A sealing member for a light-emitting device, comprising:
a sealing resin formed on a light-emitting element; and
a plurality of silicone members which comprise at least one organic
fluorescent substance, formed in said sealing resin.
23. A sealing member according to claim 22, wherein said plurality of
silicone members are coated with said sealing resin.
Description
The present application is based on Japanese Patent Application No.
2001-182543, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a light-emitting device and particularly
to a light-emitting device using a light-emitting element emitting light
in an ultraviolet region and at least one kind of fluorescent substance in
combination.
2. Description of the Related Art
There is known a light-emitting device of the type in which a
light-emitting element and at least one kind of fluorescent substance
which is excited by light emitted from the light-emitting element to
thereby generate fluorescence are used in combination so that light in a
color different from the original color of light emitted from the
light-emitting element is emitted from the light-emitting device.
Particularly with the advance of the development of a light-emitting
element capable of emitting light in an ultraviolet region, a trial to
develop a light-emitting device capable of emitting high-luminance light
has been made by using high-energy light emitted from the light-emitting
element for excitation of the fluorescent substance.
For example, a light-emitting device using a light-emitting element for
emitting light in an ultraviolet region and at least one kind of
fluorescent substance in combination has been disclosed in Japanese Patent
Publication No. 2000-208818. According to this publication, there is a
proposal for a light-emitting device which is formed so that a
light-emitting element for emitting light in an ultraviolet region is
sealed with a silicone resin containing at least one kind of organic
fluorescent substance dispersed therein.
When light in an ultraviolet region is used, it is necessary to consider
particularly photo-deterioration of the member for sealing the
light-emitting element. In the light-emitting device described in the
publication, a silicone resin which is a material hardly deteriorated by
light in an ultraviolet region is used as a sealing member to thereby
prevent photo-deterioration of the sealing member.
The silicone resin is, however, low in durability against external impact
because it is a soft material compared with an epoxy resin generally used
as a member for sealing the light-emitting element. For this reason, both
impact resistance and durability of the light-emitting element are
lowered.
On the other hand, the organic fluorescent substance is used in the
light-emitting device. Generally, it is thought that the organic
fluorescent substance is high in light converting efficiency but is easily
deteriorated by oxidization because it is highly reactive to oxygen or the
like. Hence, when the organic fluorescent substance is dispersed into the
sealing member uniformly as in the light-emitting device, the problem of
deterioration due to oxidization arises because a part of the fluorescent
substance is exposed to the outside. The deterioration of the fluorescent
substance causes reduction in luminance of the light-emitting device and
change in the emission color. Particularly when light in a visible region
is emitted from the light-emitting element in addition to light in an
ultraviolet region used for excitation of the fluorescent substance so
that light obtained by mixing the light in the visible region with
fluorescence generated by the fluorescent substance is radiated out, color
balance is collapsed by the deterioration of the fluorescent substance so
that the color of the light radiated out changes remarkably.
The surroundings of the silicone resin containing the organic fluorescent
substance dispersed in the silicone resin may be coated with an epoxy
resin so that both improvement in strength against external impact and
prevention of deterioration of the organic fluorescent substance due to
oxidization can be attained. In this case, however, an exposed portion of
the fluorescent substance in the surface of the silicone resin reacts with
the epoxy resin. As a result, a problem in reduction of luminance and
change of the emission color caused by the deterioration of the
fluorescent substance rises again.
In addition, generally, the amount of the organic fluorescent substance to
be added can be hardly adjusted due to its property compared with an
inorganic fluorescent substance. Hence, it is difficult to produce
light-emitting devices uniform in the emission color.
SUMMARY OF THE INVENTION
The present inventors have made eager examination to solve the problem. As
a result, the following configuration has been drawn as a conclusion. That
is, the configuration of the invention is as follows.
A light-emitting device including:
a light-emitting element;
a sealing member for covering a light release side of the light-emitting
element; and
a silicone member containing at least one organic fluorescent substance and
added into the sealing member.
According to this configuration, the organic fluorescent substance is added
into the sealing member in a state in which the organic fluorescent
substance is contained in the silicone members. Hence, a material
excellent in impact resistance, such as an epoxy resin, can be used as the
sealing member. Hence, the light-emitting device can be formed with high
impact resistance and high durability. Moreover, because the silicone
members containing the organic fluorescent substance are coated with the
sealing member, deterioration of the organic fluorescent substance due to
exposure to the outside can be suppressed as sufficiently as possible.
Moreover, because the organic fluorescent substance exists in the sealing
member in a state in which the organic fluorescent substance is contained
in the silicone members, the reaction between the sealing member and the
organic fluorescent substance is suppressed so that deterioration of the
fluorescent substance due to the reaction is suppressed. In this manner,
deterioration of the fluorescent substance due to the external environment
and the sealing member can be prevented. The light-emitting device can be
provided as a device causing little change in the emission color with the
passage of time.
In addition, because the organic fluorescent substance is contained in the
silicone members, handling property is improved to thereby make it easy to
adjust the amount of the fluorescent substance to be added. Hence,
light-emitting devices uniform in quality (emission color) can be
produced.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a view showing a round type LED 1 as an embodiment of the
invention.
FIG. 2 is a schematic sectional view of a light-emitting element used in
the LED;
FIG. 3 is a view showing an LED as an example in which silicone balls are
dispersed in a sealing resin;
FIG. 4 is a view showing an SMD type LED as another embodiment of the
invention;
FIG. 5 is a view showing an SMD type LED as a further embodiment of the
invention; and
FIG. 6 is a view showing an SMD type LED as a further embodiment of the
invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A light-emitting element exhibiting a main emission peak wavelength in a
wavelength range of not longer than 500 nm is used as the light-emitting
element. That is, a light-emitting element emitting light in a blue region
to an ultraviolet region is used. Preferably, a light-emitting element
exhibiting a main emission peak wavelength in a wavelength range of not
longer than 450 nm may be used. For example, a light-emitting element
exhibiting a main emission peak wavelength in a wavelength range of from
360 nm to 450 nm or a light-emitting element exhibiting a main emission
peak wavelength in a wavelength range of from 360 nm to 410 nm may be
used. Especially preferably, a light-emitting element exhibiting a main
emission peak wavelength in a wavelength range of from 360 nm to 400 nm
may be used. Light in the wavelength range can excite the fluorescent
substance (which will be described later) with high efficiency so that
light is emitted from the fluorescent substance. It is a matter of course
that a light-emitting element further exhibiting at least one additional
emission peak wavelength in a wavelength range different from the
aforementioned wavelength range may be used. In addition, a light-emitting
element exhibiting a plurality of emission peak wavelengths in the
aforementioned wavelength range maybe used. When, for example, a
light-emitting element capable of emitting light in a visible region as
well as capable of emitting light in an ultraviolet region is used, the
light in the ultraviolet region can be used for excitation of the
fluorescent substance on one hand and the light in the visible region can
be used as a part of light radiated out on the other hand. In such a
configuration, fluorescence generated by the fluorescent substance and
visible light emitted from the light-emitting element are mixed with each
other so that the mixed light is radiated out from the light-emitting
device. When, for example, a light-emitting element capable of emitting
both ultraviolet light and blue light is used in combination with a
fluorescent substance which is excited by the ultraviolet light to
generate green or red fluorescence, light-emitting devices diversified in
emission color can be formed.
For selection of the light-emitting element, the excitation peak and
fluorescence color of the (organic or inorganic) fluorescent substance
(which will be described later) and the color of light emitted from the
light-emitting device as a whole are taken into consideration.
A plurality of light-emitting elements may be used. In this case,
light-emitting elements different in emission wavelength (emission color)
can be used, so that the color of light emitted from the light-emitting
device as a whole can be changed or adjusted.
The material for forming the light-emitting element is not particularly
limited. A light-emitting element having Group III nitride compound
semiconductor layers, that is, a Group III nitride compound semiconductor
light-emitting element can be preferably used. Group III nitride compound
semiconductors are represented by the general formula Al.sub.x Ga.sub.y
In.sub.1-x-y N (0.ltoreq.X.ltoreq.1, 0.ltoreq.Y.ltoreq.1,
0.ltoreq.X+Y.ltoreq.1), which includes so-called binary compounds such as
Al.sub.x N, GaN and InN, and so-called ternary compounds such as Al.sub.x
Ga.sub.1-x N, Al.sub.x In.sub.1-x N and Ga.sub.x In.sub.1-x N
(0<x<1). The group III elements may be partially replaced by boron
(B), thallium (Tl), etc. The nitrogen (N) maybe partially replaced by
phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), etc. An
element-functional portion of the light-emitting element is preferably
made of one member selected from the binary or ternary Group III nitride
compound semiconductors.
Each of the Group III nitride compound semiconductors may contain any
optional dopant. Si, Ge, Se, Te, C, etc. may be used as n-type impurities.
Mg, Zn, Be, Ca, Sr, Ba, etc. may be used as p-type impurities.
Incidentally, after doped with p-type impurities, the Group III nitride
compound semiconductor may be subjected to electron beam irradiation,
plasma irradiation or heating in a furnace.
Each of the Group III nitride compound semiconductors maybe formed by a
metal organic chemical vapor deposition method (MOCVD method) or may be
formed by a known method such as a molecular beam epitaxy method (MBE
method), a halide vapor phase epitaxy method (HVPE method), a sputtering
method, an ion-plating method, or an electron shower method.
The material of the substrate on which the Group III nitride compound
semiconductor layers will be grown is not particularly limited if the
Group III nitride compound semiconductor layers can be grown on the
substrate. Examples of the material of the substrate which can be used
include sapphire, spinel, silicon, siliconcarbide, zincoxide, gallium
phosphide, galliumarsenide, magnesiumoxide, manganese oxide, and Group III
nitride compound semiconductor monocrystal. Particularly, a sapphire
substrate is preferably used. Further particularly, a surface a of the
sapphire substrate is preferably used.
Examples of the material of the sealing member include epoxy resin,
silicone resin, silicone rubber, silicone elastomer, urea resin, and
glass. Although it is a matter of course that these materials can be used
singly, at least two materials optionally selected from these materials
may be used. Particularly, epoxy resin may be preferably used from the
point of view of handling property and general-purpose property. When
silicone resin, silicone rubber or silicone elastomer is to be used, it is
preferable that the surface of the sealing member (the surface exposed to
the outside) is coated with a material high in impact resistance. For
example, the surface of the sealing member can be coated with a molded
epoxy resin.
The sealing member is disposed so that the light-release side of the
light-emitting element is covered with the sealing member. That is, light
released from the light-emitting element is radiated out through the
sealing member. A layer made of a material different from the material of
the sealing member may be provided between the light-emitting element and
the sealing member. For example, after a silicone resin is applied onto
the surface of the light-emitting element, a sealing member of an epoxy
resin may be formed on the silicone resin.
A light-diffusing agent may be added to the sealing member. When the
light-diffusing agent is used, diffusion of light in the sealing member is
promoted. Hence, the fluorescent substance can be efficiently irradiated
with light emitted from the light-emitting element. When a light-emitting
element also emits visible light or when a plurality of kinds of
fluorescent substances are used, color mixing of the visible light emitted
from the light-emitting element or fluorescence generated from each
fluorescent substance can be promoted so that reduction in emission
unevenness can be attained. Examples of the light-diffusing agent which
can be used include titanium oxide, titanium nitride, tantalum nitride,
aluminum oxide, silicon oxide, and barium titanate. A colorant may be also
added to the sealing member. The colorant is used for preventing the
organic fluorescent substance from exhibiting the color peculiar to the
fluorescent substance.
Silicone members containing at least one kind of organic fluorescent
substance are added into the sealing member. The organic fluorescent
substance used is not particularly limited on kind if it can be excited by
light emitted from the light-emitting element to thereby generate
fluorescence. Examples of the organic fluorescent substance which can be
used include: stilbene pigments such as 1,4-bis(2-methylstyryl)benzene
(Bis-MSB) and trans-4, 4'-diphenylstilbene (DPS); coumarin pigments such
as 7-hydroxy-4-methylcoumarin (coumarin 4); BOQP; PBBO; BOT; and POPOP.
Each of these fluorescent substances exhibits blue emission color.
Further, DPOT, brilliantsulfoflavine FF, basic yellow HG, SINLOIHI COLOR
FZ-5005 (made by Sinloihi Co., Ltd.), etc. maybe us ed as the organic
fluorescent substance. Each of these fluorescent substances exhibits
yellow or green emission color. Further, eosine, rhodamine 6G, rhodamine
B, NKP-8303 (made by Nippon Keikou Kagaku Company), etc. may be used as
the organic fluorescent substance. Each of these fluorescent substances
exhibits yellow or red emission color. Further, polymethyl methacrylate
(PMMA) obtained by polymerization and solidification of TB(EDTA)SSA,
EuTTA, etc. dissolved in methyl methacrylate may be used.
Incidentally, a plurality of kinds of organic fluorescent substances may be
used in combination. In this case, the plurality of kinds of organic
fluorescent substances may be mixed before contained in the silicone
members or may be contained in silicone members individually and
respectively.
Silicone resin, silicone rubber or silicone elastomer can be used as
silicone. Particularly, silicone resin is preferably used.
The silicone members containing the organic fluorescent substance can be
prepared, for example, by impregnating cured silicone with the organic
fluorescent substance or by mixing the organic fluorescent substance with
uncured silicone. In the former case, silicone is molded into a suitable
shape and size in advance. The silicone molded article obtained thus is
impregnated with the organic fluorescent substance through the surface of
the silicone molded article. For example, the silicone molded article is
immersed in a solution containing the organic fluorescent substance
dissolved therein, for a predetermined time. On the other hand, in the
latter case, after the organic fluorescent substance is mixed with uncured
silicone, the silicone is cured to obtain a suitable shape and size.
The shape and size of each silicone member is not particularly limited. In
consideration of handling property, a spherical shape (ball shape) with a
diameter of from 1 .mu.m to 50 .mu.m is preferably used. Especially, a
spherical shape with a diameter of from 1 .mu.m to 10 .mu.m is preferably
used. Because the size of an inorganic fluorescent substance generally
used is of the order of microns, the silicone members having the diameter
in this range can be handled in the same manner as the inorganic
fluorescent substance. This means that it is a matter of course that the
amount of the silicone members to be added, that is, the amount of the
organic fluorescent substance to be added can be adjusted easily, and that
the amount of the organic fluorescent substance to be added and the amount
of the inorganic fluorescent substance to be added can be adjusted easily
when the inorganic fluorescent substance is used together with the organic
fluorescent substance, as will be described later.
The silicone members containing the organic fluorescent substance are added
into the sealing member in a state in which the silicone members are
dispersed in the sealing member uniformly or localized in a partial region
of the sealing member. When the silicone members are localized on the
light-emitting element side, the organic fluorescent substance can be
efficiently irradiated with light emitted from the light-emitting element.
To add and localize the silicone members onto the light-emitting element
side, for example, the (light-release side) surface of the light-emitting
element is coated with a small amount of the sealing member containing the
silicone members dispersed therein, and then the sealing member containing
no silicone members is laminated thereon. As another method, a plurality
of sealing members different in the amount of the silicone members to be
added may be prepared and laminated successively so that the amount of the
silicone members to be added (that is, the amount of the organic
fluorescent substance to be added) can be changed gradually as the
location becomes farther from the light-emitting element side. As a
further method, a plurality of sealing members into which silicone members
containing different kinds of organic fluorescent substances are added
respectively may be prepared and laminated successively.
In addition to the organic fluorescent substance, an inorganic fluorescent
substance may be used. The inorganic fluorescent substance can be used in
a state in which it is added into the sealing member. As another method, a
different sealing member may be prepared so that the inorganic fluorescent
substance can be added into the sealing member. When, for example, use of
the inorganic fluorescent substance makes it possible to obtain more
efficient fluorescence in a specific fluorescent color than use of the
organic fluorescent substance in the case where a plurality of fluorescent
substances are used for externally radiating fluorescence obtained by
mixing the fluorescence emitted by the plurality of fluorescent
substances, it is preferable that the inorganic fluorescent substance is
used for the specific fluorescent color. For example, a red organic
fluorescent substance and a green or blue inorganic fluorescent substance
may be used in combination. When a suitable fluorescent substance good in
excitation efficiency is used in accordance with the color of
fluorescence, light emitted from the light-emitting element can be
utilized efficiently so that luminance of the light-emitting device can be
improved.
Examples of the inorganic fluorescent substance which can be used include:
fluorescent substances exhibiting red emission color, such as
6MgO.As.sub.2 O.sub.5 :Mn.sup.4+, Y(PV)O.sub.4 :Eu, CaLa.sub.0.1
Eu.sub.0.0 Ga.sub.3 O.sub.7, BaY.sub.0.0 Sm.sub.0.1 Ga.sub.3 O.sub.7,
Ca(Y.sub.0.5 Eu.sub.0.5)(Ga.sub.0.5 In.sub.0.5).sub.3 O.sub.7, Y.sub.3
O.sub.3 :Eu, YVO.sub.4 :Eu, Y.sub.2 O.sub.2 :Eu, 3.5MgO. 0.5MgF.sub.2
GeO.sub.2 :Mn.sup.4+, and (Y.Cd)BO.sub.2 :Eu; fluorescent substances
exhibiting blue emission color, such as (Ba, Ca, Mg).sub.5
(PO.sub.4).sub.3 Cl:Eu.sup.2+, (Ba, Mg).sub.2 Al.sub.16 O.sub.27
:Eu.sup.2+, Ba.sub.3 MgSi.sub.2 O.sub.8 :Eu.sup.2+, BaMg.sub.2 Al.sub.16
O.sub.27 :Eu.sup.2+, (Sr, Ca).sub.10 (PO.sub.4).sub.6 Cl.sub.2 :Eu.sup.2+,
(Sr, Ca).sub.10 (PO.sub.4).sub.6 Cl.sub.2.nB.sub.2 O.sub.3 :Eu.sup.2+,
Sr.sub.10 (PO.sub.4).sub.6 Cl.sub.2 :Eu.sup.2+, (Sr, Ba, Ca).sub.5
(PO.sub.4).sub.3 Cl:Eu.sup.2+, Sr.sub.2 P.sub.2 O.sub.7 :Eu, Sr.sub.5
(PO.sub.4).sub.3 Cl:Eu, (Sr, Ca, Ba).sub.3 (PO.sub.4).sub.6 Cl:Eu,
SrO.P.sub.2 O.sub.5.B.sub.2 O.sub.5 :Eu, (BaCa).sub.5 (PO.sub.4).sub.3
Cl:Eu, SrLa.sub.0.95 Tm.sub.0.05 Ga.sub.3 O.sub.7, ZnS:Ag, GaWO.sub.4,
Y.sub.2 SiO.sub.5 :Ce, ZnS:Ag, Ga, Cl, Ca.sub.2 B.sub.4 OCl:Eu.sup.2+,
BaMgAl.sub.4 O.sub.3 :Eu.sup.2+, and fluorescent substances represented by
the general formula (Ml, Eu).sub.10 (PO.sub.4).sub.5 Cl.sub.2 (in which Ml
is at least one element selected from the group consisting of Mg, Ca, Sr,
and Ba); and fluorescent substances exhibiting green emission color, such
as Y.sub.2 SiO.sub.5 :Ce.sup.3+, Tb.sup.3+, Sr.sub.2 Si.sub.3
O.sub.8.2SrCl.sub.2 :Eu, BaMg.sub.2 Al.sub.16 O.sub.27 :Eu.sup.2+,
Mn.sup.2+,ZnSiO.sub.4 :Mn, Zn.sub.2 SiO.sub.4 :Mn, LaPO.sub.4 :Tb,
SrAl.sub.2 O.sub.4 :Eu, SrLa.sub.0.2 Tb.sub.0.8 Ga.sub.3 O.sub.7,
CaY.sub.0.9 Pr.sub.0.1 Ga.sub.3 O.sub.7, ZnGd.sub.0.8 Ho.sub.0.2 Ga.sub.3
O.sub.7, SrLa.sub.0.6 Tb.sub.0.4 Al.sub.3 O.sub.7, ZnS:Cu, Al, (Zn,
Cd)S:Cu, Al, ZnS:Cu, Au, Al, Zn.sub.2 SiO.sub.4 :Mn, ZnSiO.sub.4 :Mn,
ZnS:Ag, Cu, (Zn.Cd)S:Cu, ZnS:Cu, GdOS:Tb, LaOS:Tb, YSiO.sub.4 :Ce.Tb,
ZnGeO.sub.4 :Mn, GeMgAlO:Tb, SrGaS:Eu.sup.2+, ZnS:Cu.Co, MgO.nB.sub.2
O.sub.3 :Ge, Tb, LaOBr:Tb, Tm, and La.sub.2 O.sub.2 S:Tb. Further,
YVO.sub.4 :Dy exhibiting white emission color or CaLu.sub.0.5 Dy.sub.0.5
Ga.sub.3 O.sub.7 exhibiting yellow emission color may be used.
In addition to the sealing member (hereinafter referred to as "first
sealing member"), a second sealing member may be used. The second sealing
member is formed between the light-emitting element and the first sealing
member or the surface of the first sealing member is covered with the
second sealing member. Epoxy resin, silicone resin, urea resin or glass as
listed in the description of the first sealing member may be used as the
material of the second sealing member. For example, the first sealing
member is made of a silicone resin and the second sealing member is made
of an epoxy resin so that the first sealing member is covered with the
second sealing member.
The second sealing member may contain at least one kind of fluorescent
substance (inclusive of an organic fluorescent substance and an inorganic
fluorescent substance), a light-diffusing agent, and/or a colorant. The
second sealing member may further contain an ultraviolet absorber. When
such an ultraviolet absorber is used, light in an ultraviolet region which
is not used for excitation of the fluorescent substance can be absorbed to
the second sealing member so that light in the ultraviolet region can be
prevented from being radiated out. For example,
2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole can be used as
the ultraviolet absorber.
The configuration of the invention will be described below more in detail
in connection with embodiments thereof.
(Embodiment 1)
FIG. 1 is a view showing a round type LED 1 as an embodiment of the
invention. The LED 1 emits white light and, for example, can be used in
combination with a light guide for forming a surface light source or a
linear light source. Further, the LED 1 can be used for various kinds of
display devices.
FIG. 2 is a sectional view schematically showing a light-emitting element
10 used in the LED 1. The light-emitting element 10 has a sapphire
substrate, and a plurality of Group III nitride compound semiconductor
layers laminated on the sapphire substrate. The light-emitting element 10
exhibits an emission peak at a wave length of about 380 nm. Specifications
of respective layers in the light-emitting element 10 are as follows.
Layer Composition
p-type layer 15 p-GaN:Mg
Light-emitting Inclusive of InGaN layer
layer-containing layer 14
n-type layer 13 n-GaN:Si
Buffer layer 12 AlN
Substrate 11 Sapphire
The n-type layer 13 of GaN doped with Si as n-type impurities is formed on
the substrate 11 through the buffer layer 12. Although this embodiment
shows the case where a sapphire substrate is used as the substrate 11, the
invention is not limited thereto. Examples of the material of the
substrate 11 which can be used include sapphire, spinel, silicon, silicon
carbide, zinc oxide, gallium phosphide, gallium arsenide, magnesium oxide,
manganese oxide, and Group III nitride compound semiconductor monocrystal.
Although this embodiment also shows the case where the buffer layer 12 is
made of AlN by an MOCVD method, the invention is not limited thereto. For
example, GaN, InN, AlGaN, InGaN, or AlInGaN may be used as the material of
the buffer layer 12. A molecular beam epitaxy method (MBE method), a
halide vapor phase epitaxy method (HVPEmethod), a sputtering method, an
ion-plating method, an electron shower method, etc. may be used as the
method for producing the buffer layer 12. When Group III nitride compound
semiconductor is used as the substrate 11, the buffer layer 12 can be
omitted.
The substrate and the buffer layer may be removed in accordance with
necessity after the formation of the semiconductor element.
Although this embodiment shows the case where the n-type layer 13 is made
of GaN, the invention may be applied also to the case where AlGaN, InGaN
or AlInGaN is used as the material of the n-type layer 13.
Further, although this embodiment shows the case where the n-type
semiconductor layer 13 is doped with Si as n-type impurities, the
invention may be applied also to the case where Ge, Se, Te, C, or the
like, is used as n-type impurities.
The n-type layer 13 may be of a double-layer structure with an n.sup.-
layer of low electron density on the light-emitting layer-containing layer
14 side and an n.sup.+ layer of high electron density on the buffer layer
12 side.
The light-emitting layer-containing layer 14 may contain a quantum well
structure (multiple quantum well structure or single quantum well
structure). Further, the structure of the light-emitting element may be of
a single hetero type, a double hetero type or a homo-junction type.
The light-emitting layer-containing layer 14 may contain a Group III
nitride compound semiconductor layer provided on the p-type layer 15 side,
doped with an acceptor such as magnesium and having a wide band gap. This
arrangement is made for effectively preventing electrons injected into the
light-emitting layer-containing layer 14 from diffusing into the p-type
layer 15.
The p-type layer 15 made of GaN doped with Mg as p-type impurities is
formed on the light-emitting layer-containing layer 14. Alternatively, the
p-type layer 15 may be made of AlGaN, InGaN or InAlGaN. Zn, Be, Ca, Sr or
Ba may be used as p-type impurities instead.
Further, the p-type layer 15 may be of a double-layer structure with a
p.sup.- layer of low hole density on the light-emitting layer-containing
layer 14 side and a p.sup.+ layer of high hole density on the electrode
side.
In the light-emitting diode configured as described above, each of the
Group III nitride compound semiconductor layers may be formed by an MOCVD
method in a general condition or may be formed by a method such as a
molecular beam epitaxy method (MBE method), a halide vapor phase epitaxy
method (HVPE method), a sputtering method, an ion-plating method, or an
electron shower method.
The n electrode 19 is composed of two layers of Al and V. After the p-type
layer 15 is formed, the p-type layer 15, the light-emitting
layer-containing layer 14 and the n-type layer 13 are partially removed by
etching. In this condition, the n electrode 19 is formed on the n-type
layer 13 by vapor deposition.
The light-transmissive electrode 17 is a thin film containing gold and is
laminated on the p-type layer 15. The p electrode 18 is also made of a
material containing gold and is formed on the light-transmissive electrode
17 by vapor deposition.
After the respective semiconductor layers and the respective electrodes are
formed by these steps, a step of separating the substrate into chips is
carried out.
A reflecting layer may be provided between the light-emitting
layer-containing layer 14 and the substrate 11 or on a surface of the
substrate 11 where the semiconductor layers are not formed. When the
reflecting layer is provided, light emitted from the light-emitting
layer-containing layer 14 toward the substrate side can be reflected
toward the light-extracting direction efficiently. As a result,
improvement of light-emitting efficiency can be attained. The reflecting
layer can be formed of at least one member selected from the group
consisting of titanium nitride, zirconium nitride, and tantalum nitride.
Alternatively, the reflecting layer may be made of a single metal selected
from the group consisting of Al, In, Cu, Ag, Pt, Ir, Pd, Rh, W, Mo, Ti,
and Ni, or may be made of an alloy composed of at least two metals
optionally selected from the group.
The light-emitting element 10 is mounted, through an adhesive agent, into a
cup-like portion 25 provided in a lead frame 20 . The adhesive agent is
silver paste which contains an epoxy resin, and silver as a filler mixed
with the epoxy resin. When such silver paste is used, heat can be better
radiated from the light-emitting element 10. Incidentally, the silver
paste may be replaced by another known adhesive agent such as transparent
paste or white paste.
The p electrode 18 and the n electrode 19 in the light-emitting element 10
are wire-bonded to lead frames 21 and 20 by wires 41 and 40 respectively.
Then, the cup-like portion 25 is filled with an epoxy resin 27 containing
silicone balls 30, 31 and 32 which are impregnated with different kinds of
organic fluorescent substances respectively and which are dispersed into
the epoxy resin 27 uniformly (hereinafter, referred to as "fluorescent
substance resin 27"). The silicone balls 30, 31 and 32 are impregnated
with a red organic fluorescent substance NKP-8303 (made by Nippon Keikou
Kagaku Company), a green organic fluorescent substance SINLOIHI COLOR
FZ-5005 (Sinloihi Co., Ltd.) and a blue organic fluorescent substance
1,4-bis(2-methylstyryl)benzene (Bis-MSB) respectively. The silicone balls
30, 31 and 32 are produced by the following method. First, liquid silicone
is cured while molded into a spherical shape (silicone ball) with a
diameter of about 5.mu.m. The silicone ball obtained thus is immersed in a
solution in which an organic fluorescent substance to be used for
impregnation is dissolved, for about 3hours. Incidentally, the immersion
time is adjusted suitably in consideration of the impregnation efficiency.
The amount of each of the three kinds of silicone balls 30, 31 and 32 to be
added to the epoxy resin is determined in consideration of the amount of a
corresponding kind of organic fluorescent substance contained in the
silicone balls, the fluorescence generating efficiency of the organic
fluorescent substance, the color of light emitted from the light-emitting
device 1, and so on.
Although this embodiment has shown the case where a red organic fluorescent
substance, a green organic fluorescent substance and a blue organic
fluorescent substance, that is, three kinds of organic fluorescent
substances are used, the invention may be applied also to the case where
only one kind of organic fluorescent substance is used or two kinds of
organic fluorescent substances are used in accordance with the required
emission color.
The fluorescent substance resin layer 27 is formed by potting the epoxy
resin containing the silicone balls 30, 31 and 32 dispersed therein in the
cup-like portion 25 after mounting the light-emitting element 10 into the
cup-like portion 25. Incidentally, besides potting, the fluorescent
substance resin layer 27 may be formed by another method such as
sputtering, application, or painting.
The fluorescent substance resin layer may be formed so that the surface of
the light-emitting element 10 is coated with the fluorescent substance
resin layer. For example, the light-emitting element 10 may be dipped in
the epoxy resin containing the silicone balls 30, 31 and 32 dispersed
therein, so that the surface of the light-emitting element 10 is coated
with the fluorescent substance layer. After the dip coating, the
light-emitting element 10 may be mounted into the cup-like portion 25.
Also by this method, the surface of the light-emitting element 10 can be
coated with the fluorescent substance resin. Incidentally, besides
dipping, coating may be made by another method such as sputtering,
application, or painting.
Although this embodiment has shown the case where an epoxy resin is used as
a base material for dispersing the silicone balls 30, 31 and 32, the
invention is not limited thereto. For example, a transparent material such
as silicone (silicone resin, silicone rubber or silicone elastomer), urea
resin or glass may be used instead. Although this embodiment has shown the
case where the silicone balls 30, 31 and 32 are dispersed into the
fluorescent substance resin layer 27 uniformly, the invention may be
applied also to the case where gradients are formed in the concentration
distributions of the silicone balls 30, 31 and 32 in the fluorescent
substance resin layer 27. For example, epoxy resins different in the
concentrations of the silicone balls 30, 31 and 32 to be added is
laminated successively on the light-emitting element 10 . Although this
embodiment has shown the case where all the silicone balls are dispersed
into one epoxy resin to thereby form a fluorescent substance layer, the
invention maybe applied also to the case where epoxy resins containing
silicone balls dispersed therein respectively are prepared and dropped
into the cup-like portion 25 individually to thereby form a fluorescent
substance resin layer as a laminate of the resins containing different
silicone balls dispersed therein respectively.
The fluorescent substance resin layer 27 may contain a diffusing agent such
as titanium oxide, titanium nitride, tantalum nitride, aluminum oxide,
silicon oxide, or barium titanate.
The light-emitting element 10, part of the lead frames 20 and 21 and the
wires 40 and 41 are sealed with a sealing resin 50 made of an epoxy resin.
The material of the sealing resin 50 is not particularly limited so long
as the material is transparent. An epoxy resin is preferably used as the
material of the sealing resin 50. From the point of view of adhesion
between the sealing resin 50 and the fluorescent substance resin layer 27
and refractive index, the sealing resin 50 is preferably made of the same
material as that of the fluorescent substance resin layer 27.
The sealing resin 50 is provided for protecting the device structure. When
the shape of the sealing resin 50 is changed in accordance with the
purpose, a lens effect can be given to the sealing resin 50. For example,
the sealing resin 50 may be molded into a concave lens shape or a convex
lens shape as well as the round shape shown in FIG. 1. The shape of the
sealing resin 50 viewed from the light-extracting direction (above in FIG.
1) may be also a circular shape, an elliptic shape or a rectangular shape.
The silicone balls 30, 31 and 32 may be disposed also in the sealing resin
50.
Though not shown, a diffusing agent, and an ultraviolet absorber are
dispersed in the sealing resin 50. When the diffusing agent is used,
diffusion and color mixing of the light in the sealing resin can be
promoted so that emission unevenness can be reduced. Examples of the
diffusing agent used include titanium oxide, titanium nitride, tantalum
nitride, aluminum oxide, silicon oxide, and barium titanate. On the other
hand, when the ultraviolet absorber is used, the residual part of the
ultraviolet light which has not used for excitation of the fluorescent
substance can be prevented from being radiated out. Incidentally, either
or both of the diffusing agent and the ultraviolet absorber may be
omitted.
When the silicone balls 30, 31 and 32 are added into the sealing resin 50
as shown in FIG. 3, the fluorescent substance resin layer 27 can be
omitted. Incidentally, in FIG. 3, members the same as those in FIG. 1 are
referenced correspondingly. Also in this case, gradients may be provided
in the concentration distributions of the silicone balls 30, 31 and 32 in
the sealing resin 50 in the same manner as in the fluorescent substance
resin layer 27.
In the LED 1 configured as described above, the organic fluorescent
substances contained in the silicone balls 30, 31, 32 respectively are
irradiated with light in an ultraviolet region emitted from the
light-emitting element 10, so that the organic fluorescent substances are
excited to emit light. As a result, three types of fluorescence, that is,
red fluorescence, green fluorescence and blue fluorescence, are generated.
These types of fluorescence are mixed with a small part of visible light
emitted from the light-emitting element, so that the mixed light is
released out. As a result, white emitted light is obtained from the LED 1.
In addition to the light-emitting element 10, another light-emitting
element may be used. A light-emitting element different in emission
wavelength from the light-emitting element 10 is used as the other
light-emitting element. When the other light-emitting element is used, the
color of light emitted from the LED 1 can be changed or adjusted. Further,
a plurality of light-emitting elements 10 may be used to enhanced
luminance.
(Embodiment 2)
FIG. 4 is a sectional view of an SMD type LED 3 as another embodiment of
the invention. In Embodiment 2, members the same as those in the LED 1 of
Embodiment 1 are referenced correspondingly and the description of these
members is omitted. The LED 3 emits white light in the same manner as in
Embodiment 1. For example, the LED 3 can be used in combination with a
light guide for forming a surface light source or a linear light source.
The LED 3 can be further used for forming various kinds of display
devices.
The light-emitting element 10 is fixed to a substrate 80 by silver paste or
the like. Wires 40 and 41 connect respective electrodes of the
light-emitting element 10 to electrodes 81 and 82 provided on the
substrate 80. The reference numeral 90 designates a reflector formed as
the surroundings of the light-emitting element. The reflector 90 has a
surface provided as a specular surface.
A cup-like portion formed by the substrate 80 and the reflector 90 is
filled with a fluorescent substance resin layer 100 and a sealing resin
85. The fluorescent substance resin layer 100 is made of a silicone resin
containing silicone balls 30 and 32 and an inorganic fluorescent substance
37 dispersed therein. The silicone balls 30 and 32 are made of spherical
silicone resins impregnated with red and blue organic fluorescent
substances respectively as described above. The inorganic fluorescent
substance 37 is a green fluorescent substance Y.sub.2 SiO.sub.5
:Ce.sup.3+, Tb.sup.3+. The fluorescent substance resin layer 100 is formed
by a method such as a potting method after the light-emitting element 10
is mounted. The sealing resin 85 is made of an epoxy resin. The sealing
resin 85 is formed by the same method as the method for forming the
fluorescent substance resin layer 100 after the fluorescent substance
resin layer 100 is formed.
In the LED 3 configured as described above, when light in an ultraviolet
region passes through the fluorescent substance resin layer 100 , the
light in the ultraviolet region emitted from the light-emitting element 10
excites the organic fluorescent substances contained in the silicone balls
30 and 32 and the inorganic fluorescent substance 37 to thereby emit
light. The fluorescence generated thus and visible light emitted from the
light-emitting element are mixed with each other in terms of the color of
light, so that white light is radiated out as a whole.
In the LED 3 shown in FIG. 4, the fluorescent substance resin layer 100 and
the sealing resin 85 are provided separately. As shown in FIG. 5, silicone
balls 30 and 32 and the inorganic fluorescent substance 37 may be
dispersed in a sealing resin 101. Incidentally, in FIG. 5, members the
same as those in FIG. 4 are referenced correspondingly.
FIG. 6 shows an example of the configuration of an SMD type LED 5 without
using any reflector 90. In the LED 5, a sealing resin 102 shaped like an
approximate rectangle in section is formed so that the light-emitting
element 10 is covered with the sealing resin 102. The sealing resin 102 is
made of an epoxy resin containing silicone balls 30 and 32 and an
inorganic fluorescent substance 37 dispersed therein. The sealing resin
102 can be formed by molding using a desired mold after the light-emitting
element 10 is mounted on a substrate 80. Alternatively, a sealing resin
102 molded into a desired shape may be prepared so that the sealing resin
102 is bonded to the substrate 80 so that the light-emitting element 10 is
covered with the sealing resin 102.
Incidentally, like the LED 1 obtained in Embodiment 1, the sealing resin 85
in the LED 3 shown in FIG. 4, the fluorescent resin layer 100 and/or the
sealing resin 85 in the LED 4 shown in FIG. 5, and the sealing resin 102
in the LED 5 shown in FIG. 6 may contain either a diffusing agent or an
ultraviolet absorber or may contain at least two kinds of diffusing agents
and ultraviolet absorbers in combination.
The invention is not limited at all to the description of the mode for
carrying out the invention and the description of the embodiments. The
invention includes various modifications that can be conceived easily by
those skilled in the art, without departing from the description of the
scope of claim.
*
