Title: Red light emitting phosphor, its production and light emitting device
Abstract: As a red light emitting phosphor capable of efficiently emitting red light at a high luminance in response to exciting light having a wavelength of 350-420 nm, and practically used in a light emitting device for red display or a light emitting device for white or intermediate color display in combination with green and blue light emitting phosphors, the invention provides a red light emitting phosphor capable of emitting red light upon excitation with light having a wavelength of 350-420 nm and having compositional formula (1):
AEuxLn(1-x)M2O8 (1)
wherein A is at least one element selected from among Li, Na, K, Rb and Cs, Ln is at least one element selected from among Y and rare earth elements exclusive of Eu, M is at least one element selected from among W and Mo, and x is a positive number satisfying 0<x≦1; and a red light emitting phosphor having compositional formula (2):
D0.5EuyLn(1-y)M2O8 (2)
wherein D is at least one element selected from among Mg, Ca, Sr and Ba, Ln is at least one element selected from among Y and rare earth elements exclusive of Eu, M is at least one element selected from among W and Mo, and y is a positive number satisfying 0<y≦1. Methods for preparing the red light emitting phosphors, and light emitting devices using the red light emitting phosphors are also provided.
Patent Number: 6,982,523 Issued on 01/03/2006 to Odaki
| Inventors:
|
Odaki; Tsutomu (Nishishirakawa-gun, JP)
|
| Assignee:
|
Kabushiki Kaisha Fine Rubber Kenkyuusho (Nishishirakawa-gun, JP)
|
| Appl. No.:
|
352131 |
| Filed:
|
January 28, 2003 |
| Current U.S. Class: |
313/503; 313/498; 313/499; 313/501; 313/502; 313/512; 257/89; 257/90; 257/98; 257/100; 252/301.4R; 252/301.4P; 252/301.5 |
| Current Intern'l Class: |
H01J 1/62 (20060101); H01J 63/04 (20060101); C09K 11/68 (20060101); H01L 29/20.1 (20060101); H01L 29/22.7 (20060101) |
| Field of Search: |
252/3014 R,301.5,301.4
257/89,90,98,100
313/499-502
|
References Cited [Referenced By]
U.S. Patent Documents
| 3652956 | Mar., 1972 | Pinnow et al.
| |
| 6066861 | May., 2000 | Hohn et al.
| |
| 6717348 | Apr., 2004 | Takahashi.
| |
| 2001/0050371 | Dec., 2001 | Okaki et al.
| |
| Foreign Patent Documents |
| 11-246857 | Sep., 1999 | JP.
| |
| 2000/-144130 | May., 2000 | JP.
| |
| 2001/-267632 | Sep., 2001 | JP.
| |
Other References
F. Shi et al., J. Phys. Chem Solids., vol. 59, No. 1, pp. 105-110 (1998).
J.P.M. Van Viiet, J. Solid State Chem, 76, pp. 160-166 (1998).
|
Primary Examiner: Patel; Nimeshkumar D.
Assistant Examiner: Hodges; Matt
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt, P.C.
Claims
What is claimed is:
1. A red light emitting phosphor capable of emitting red light upon excitation
with light having a wavelength of 350 to 420 nm, characterized by having a composition
of compositional formula (1):
AEu
xLn
(1-x)M
2O
8 (1)
wherein A is at least one element selected from the group consisting of Li, Na,
K, Rb and Cs, and is partially substituted with at least one element selected from
the group consisting of Mg, Ca, Sr and Ba to be added as a co-activator,
Ln is at least one element selected from the group consisting of Y and rare earth
elements exclusive of Eu,
M is at least one element selected from the group consisting of W and Mo, and
x is a positive number satisfying 0<x≦1.
2. A red light emitting phosphor capable of emitting red light upon excitation
with light having a wavelength of 350 to 420 nm, characterized by having a composition
of compositional formula (2):
D
0.5Eu
yLn
(1-y)M
2O
8 (2)
wherein D is at least one element selected from the group consisting of Mg, Ca,
Sr and Ba,
Ln is at least one element selected from the group consisting of Y and rare earth
elements exclusive of Eu,
M is at least one element selected from the group consisting of W and Mo, and
y is a positive number satisfying 0<y≦1.
3. The red light emitting phosphor of 2, characterized in that Ln in the formula
is at least one element selected from the group consisting of Y, La, Gd and Lu.
4. The red light emitting phosphor of 2, characterized in that Eu constituting
the red light emitting phosphor is in the form of trivalent europium ions (Eu
3+)
which are arranged in a two- or one-dimensional array.
5. A method for preparing the red light emitting phosphor of claim 1, characterized
by comprising the steps of mixing raw materials containing elements constituting
the red light emitting phosphor, firing the resulting mixture, and washing the
fired product with an aqueous alkali solution.
6. A method for preparing the red light emitting phosphor of claim 2, characterized
by comprising the steps of mixing raw materials containing elements constituting
the red light emitting phosphor, firing the resulting mixture, and washing the
fired product with an aqueous acid solution.
7. A light emitting device comprising a semiconductor light emitter capable of
emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that the red light emitting phosphor of 2 is dispersed in the encapsulant.
8. A light emitting device comprising a semiconductor light emitter capable of
emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that a fluorescent layer containing the red light emitting phosphor
of 2 is disposed in an optical path of the light from the semiconductor light emitter.
9. A light emitting device comprising a semiconductor light emitter capable of
emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that a fluorescent layer containing the red light emitting phosphor
of 2 is disposed on the semiconductor light emitter or the encapsulant.
10. A light emitting device comprising a semiconductor light emitter capable
of emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that a fluorescent layer comprising the red light emitting phosphor
of 2 dispersed in a resin, rubber, elastomer or glass is disposed on the semiconductor
light emitter or the encapsulant.
11. The red light emitting phosphor as claimed in claim 1 wherein x is a positive
number satisfying 0.3≦x≦1.
12. The red light emitting phosphor as claimed in claim 1 wherein x is a positive
number satisfying 0.5≦x≦1.
13. The red light emitting phosphor as claimed in claim 2 wherein y is a positive
number satisfying 0.3≦y≦1.
14. The red light emitting phosphor as claimed in claim 2 wherein y is a positive
number satisfying 0.5≦y≦1.
Description
BACKGROUND OF THE INVENTION
This invention relates to red light emitting phosphors capable of emitting red
light upon excitation with long-wavelength ultraviolet radiation or short-wavelength
visible light of 350 to 420 nm, methods for preparing the same, and light emitting
devices comprising the read light emitting phosphors.
Light emitting diodes (LEDs) are semiconductor light emitters adapted to produce
light by converting electrical energy into ultraviolet light, visible light, infrared
light or the like. For example, those emitters utilizing visible light are semiconductor
light emitters formed from light emitting materials such as GaP, GaAsP and GaAlAs,
and LED lamps having such emitters encapsulated with transparent resins are widely
used. Also LED lamps of the display type are often used in which light emitting
materials are secured to an upper surface of a printed circuit board or metal leads
and encased in a transparent resin casing on which numerical figures or characters
are configured.
LEDs have a long lifetime and high reliability because of semiconductor devices,
and facilitate replacement operation when used as light sources. LEDs are thus
widely used as components in portable communications equipment, personal computer
peripheral equipment, business machines, household electric appliances, audio equipment,
switches, back light sources, and display device such as bulletin boards.
The color of light emitted by the LED lamps can be altered by introducing various
powder phosphors into transparent resins with which semiconductor light emitters
are encapsulated. Depending on the intended application, any color in a wide spectrum
in the visible region from blue to red is available.
However, recently users increasingly impose a more stringent demand on the
color of such various display device, requiring display devices to have an ability
to precisely reproduce a subtle color tone. It is strongly required that a single
LED lamp emit white or any desired intermediate color light.
Attempts were then made to display white or any desired intermediate color
with a single LED lamp by applying various red, green and blue phosphors to the
surface of the semiconductor light emitter in the LED lamp, or incorporating such
various phosphors in the encapsulant or coating material of the LED lamp.
Among these phosphors, currently used typical examples of those phosphors to
be excited with long-wavelength ultraviolet radiation or short-wavelength visible
light (350 to 420 nm) include BaMg
2Al
16O
27:Eu
and (Sr,Ca,Ba)
5(PO
4)
3Cl:Eu for emission of blue
light, BaMg
2Al
16O
27:Eu,Mn and Zn
2GeO
4:Mn
for emission of green light, and Y
2O
2S:Eu, La
2O
2S:Eu
and 3.5MgO·0.5MgF
2·GeO
2:Mn for emission of red
light. Using appropriate ones of these light emitting phosphors, an emission color
over a wide range is available.
However, the above-noted red light emitting phosphors have the problem of
weak light emission to long-wavelength ultraviolet radiation and short-wavelength
visible light (350 to 420 nm), as compared with the blue and green light emitting phosphors.
Then, when whitish light is produced using lights of these wavelengths, the
proportion of the red light emitting phosphor must be increased at the sacrifice
of cost. Since white color of light is obtainable by balancing the quantities of
red, green and blue light emissions, the quantities of green and blue light emissions
must be reduced in proportion to the quantity of red light emission in order to
produce emission of a whitish light. Further, an upper limit is imposed on the
amount of phosphors used. As a result, a less quantity of white light emission
is available, giving rise to problems including a failure to produce white light
with a high luminance.
The wavelength corresponding to the excitation energy of electron pairs oxide
base compounds possess is within the ultraviolet region, and the wavelength of
long-wavelength ultraviolet radiation and short-wavelength visible light (350 to
420 nm) overlies the absorption edge of phosphors. Then, particularly for red light
emitting phosphors, there arises the problem that the quantity of light emission
of a phosphor changes significantly if the peak of emission wavelength of a semiconductor
light emitter varies.
To solve this problem, rare earth oxysulfide phosphors activated with europium
are proposed in JP-A 11-246857, JP-A 2000-144130, etc. It is reported that the
excitation wavelength for these phosphors is shifted to the longer wavelength side.
On a longer than 350 nm wavelength side, however, the absorption intensity of
these red light emitting phosphors shows a sharp decline as the wavelength becomes
longer. When a light source with an emission peak at 350 to 420 nm, for example,
a ultraviolet LED is used as an excitation light source, the quantity of emission
of a phosphor changes significantly due to variations of the wavelength of LED
emission, that is, the wavelength of excitation light, which inevitably occur for
manufacturing reasons. This results in variations of color tone when the above
phosphor is used in combination with green and blue light emitting phosphors to
produce white or intermediate color. The conventional red light emitting phosphors
are difficult to precisely reproduce a subtle color tone.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a red light emitting phosphor
which emits red light at a high efficiency and a high luminance in response to
excitation light of 350 to 420 nm wavelength, and which can be practically used
as a light emitting device for red color display or in combination with green and
blue light emitting phosphors to construct a light emitting device for white or
intermediate color display; a method for preparing the same; and a light emitting
device comprising the same.
Making extensive investigations to solve the above problems, the inventor
has found that a red light emitting phosphor represented by the compositional formula
(1) or (2) below and capable of emitting red light upon excitation with light having
a wavelength of 350 to 420 nm emits red light at a high efficiency and a high luminance
in response to excitation light of 350 to 420 nm wavelength, that is, emits red
light at a consistent intensity in response to radiation of a wavelength in the
wide range from long-wavelength ultraviolet radiation to short-wavelength visible light.
It has also been found that this red light emitting phosphor can be practically
used as a light emitting device for red color display or in combination with green
and blue light emitting phosphors to construct a light emitting device for white
or intermediate color display; and that when this red light emitting phosphor is
combined with green and blue light emitting phosphors so that the phosphors generate
light for white or intermediate color display in response to the light of the aforementioned
wavelength emitted by a semiconductor light emitter, a subtle color tone is precisely
displayed in a reproducible manner because this red light-emitting phosphor is
little affected by variations in wavelength of the exciting light.
It has further been found that when a red light emitting phosphor of compositional
formula (1) below is prepared by mixing raw materials containing elements constituting
the red light emitting phosphor, firing the resulting mixture, and washing the
fired product with an aqueous alkali solution, or when a red light emitting phosphor
of compositional formula (2) below is prepared by mixing raw materials containing
elements constituting the red light emitting phosphor, firing the resulting mixture,
and washing the fired product with an aqueous acid solution, the red light emitting
phosphor having a higher emission intensity is obtainable.
Namely, the present invention provides a red light emitting phosphor, a method
for preparing the same, and a light emitting device comprising the same, which
are defined below.
[1] A red light emitting phosphor capable of emitting red light upon excitation
with light having a wavelength of 350 to 420 nm, characterized by having a composition
of compositional formula (1):
AEu
xLn
(1-x)M
2O
8 (1)
wherein A is at least one element selected from the group consisting of Li,
Na, K, Rb and Cs, Ln is at least one element selected from the group consisting
of Y and rare earth elements exclusive of Eu, M is at least one element selected
from the group consisting of W and Mo, and x is a positive number satisfying 0<x≦1.
[2] The red light emitting phosphor of [1], characterized in that A in the compositional
formula (1) is partially substituted with at least one element selected from the
group consisting of Mg, Ca, Sr and Ba to be added as a co-activator.
[3] A red light emitting phosphor capable of emitting red light upon excitation
with light having a wavelength of 350 to 420 nm, characterized by having a composition
of compositional formula (2):
D
0.5Eu
yLn
(1-y)M
2O
8 (2)
wherein D is at least one element selected from the group consisting of Mg,
Ca, Sr and Ba, Ln is at least one element selected from the group consisting of
Y and rare earth elements exclusive of Eu, M is at least one element selected from
the group consisting of W and Mo, and y is a positive number satisfying 0<y≦1.
[4] The red light emitting phosphor of [1] or [3], characterized in that Ln in
the formula is at least one element selected from the group consisting of Y, La,
Gd and Lu.
[5] The red light emitting phosphor of [1] or [3], characterized in that Eu constituting
the red light emitting phosphor is in the form of trivalent europium ions (Eu
3+)
which are arranged in a two- or one-dimensional array.
[6] A method for preparing the red light emitting phosphor of [1], characterized
by comprising the steps of mixing raw materials containing elements constituting
the red light emitting phosphor, firing the resulting mixture, and washing the
fired product with an aqueous alkali solution.
[7] A method for preparing the red light emitting phosphor of [3], characterized
by comprising the steps of mixing raw materials containing elements constituting
the red light emitting phosphor, firing the resulting mixture, and washing the
fired product with an aqueous acid solution.
[8] A light emitting device comprising a semiconductor light emitter capable
of emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that the red light emitting phosphor of [1] or [3] is dispersed
in the encapsulant.
[9] A light emitting device comprising a semiconductor light emitter capable
of emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that a fluorescent layer containing the red light emitting phosphor
of [1] or [3] is disposed in an optical path of the light from the semiconductor
light emitter.
[10] A light emitting device comprising a semiconductor light emitter capable
of emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that a fluorescent layer containing the red light emitting phosphor
of [1] or [3] is disposed on the semiconductor light emitter or the encapsulant.
[11] A light emitting device comprising a semiconductor light emitter capable
of emitting light having a wavelength of 350 to 420 nm, enclosed in an encapsulant,
characterized in that a fluorescent layer comprising the red light emitting phosphor
of [1] or [3] dispersed in a resin, rubber, elastomer or glass is disposed on the
semiconductor light emitter or the encapsulant.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view illustrating the state where trivalent europium ions
(Eu
3+) are arranged in a two-dimensional array.
FIG. 2 is a schematic view illustrating the state where trivalent europium ions
(Eu
3+) are arranged in a one-dimensional array.
FIG. 3 is a cross-sectional view of a light emitting device according to one
embodiment of the invention, in which the red light emitting phosphor of the invention
is dispersed in an encapsulant of a bullet-shaped light emitting diode.
FIG. 4 is a cross-sectional view of a light emitting device according to one
embodiment of the invention, in which the red light emitting phosphor of the invention
is dispersed in an encapsulant of a chip-shaped light emitting diode.
FIG. 5 is a cross-sectional view of a light emitting device according to one
embodiment of the invention, in which a fluorescent layer containing the red light
emitting phosphor of the invention is disposed on a semiconductor light emitter
in a bullet-shaped light emitting diode.
FIG. 6 is a cross-sectional view of a light emitting device according to one
embodiment of the invention, in which a fluorescent layer containing the red light
emitting phosphor of the invention is disposed on a semiconductor light emitter
in a chip-shaped light emitting diode.
FIG. 7 is a cross-sectional view of a light emitting device according to one
embodiment of the invention, in which a fluorescent layer containing the red light
emitting phosphor of the invention is disposed on an encapsulant in a bullet-shaped
light emitting diode.
FIG. 8 is a cross-sectional view of a light emitting device according to one
embodiment of the invention, in which a fluorescent layer containing the red light
emitting phosphor of the invention is disposed on an encapsulant in a chip-shaped
light emitting diode.
FIG. 9 is a cross-sectional view of a light emitting device according to one
embodiment of the invention, in which a fluorescent layer is spaced apart from
LED and which is constructed such that light emitted by the fluorescent layer is reflected.
FIG. 10 is a diagram showing the emission spectra of the inventive red light
emitting phosphor LiEuW
2O
8 and Y
2O
2S:Eu.
FIG. 11 is a diagram showing the excitation spectrum for the inventive red light
emitting phosphor LiEuW
2O
8.
FIG. 12 is a diagram showing the distribution of light emitted by the light
emitting device of Example 9.
FIG. 13 is a diagram showing the distribution of light emitted by the light
emitting device of Example 10.
DETAILED DESCRIPTION OF THE INVENTION
[First Embodiment of Red Light Emitting Phosphor]
The first embodiment of the red light emitting phosphor according to the invention
is described. The first embodiment is a red light emitting phosphor capable of
emitting red light upon excitation with light having a wavelength of 350 to 420
nm and having a composition of compositional formula (1):
AEu
xLn
(1-x)M
2O
8 (1)
wherein A is at least one element selected from the group consisting of Li,
Na, K, Rb and Cs; Ln is at least one element selected from the group consisting
of Y and rare earth elements exclusive of Eu; M is at least one element selected
from the group consisting of W and Mo; and x is a positive number satisfying 0<x≦1,
preferably 0.3≦x≦1, most preferably 0.5≦x≦1.
In compositional formula (1), Ln is at least one element selected from the group
consisting of Y and rare earth elements exclusive of Eu, while Y, La, Gd and Lu
are preferred. A is preferably at least one element selected from Li and Na having
an ionic radius close to that of Eu. Of these compositions, LiEuM
2O
8
and LiEu
xY
(1-x)M
2O
8 are especially preferred.
Also preferred in the invention are those red light emitting phosphors of the
compositional formula (1) wherein A (which is at least one element selected from
the group consisting of Li, Na, K, Rb and Cs) is partially substituted with at
least one element selected from the group consisting of Mg, Ca, Sr and Ba to be
added as a co-activator. In this embodiment, the degree of substitution is preferably
less than 0.5 (atomic ratio), more preferably up to 0.3 (atomic ratio), even more
preferably up to 0.2 (atomic ratio), most preferably up to 0.1 (atomic ratio),
as expressed by the ratio of the total amount of Mg, Ca, Sr and Ba to the total
amount of Li, Na, K, Rb and Cs.
The red light emitting phosphor of compositional formula (1) can be prepared
by mixing raw materials containing elements constituting the red light emitting
phosphor, firing the resulting mixture, optionally grinding and sieving the fired
product. The fired product is preferably washed with an aqueous alkali solution
because the resulting red light emitting phosphor is capable of emitting red light
of a higher luminance. Examples of the aqueous alkali solution used herein include
an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and
an aqueous potassium hydroxide solution, with the pH being preferably 8 or higher.
Washing with an aqueous alkali solution can be carried out by immersing the fired
product in an aqueous alkali solution, optionally followed by agitation. Once washed
with the aqueous alkali solution, the fired product is separated from the aqueous
alkali solution, washed with water and dried, yielding a red light emitting phosphor.
[Second Embodiment of Red Light Emitting Phosphor]
The second embodiment of the red light emitting phosphor according to the invention
is described. The second embodiment is a red light emitting phosphor capable of
emitting red light upon excitation with light having a wavelength of 350 to 420
nm and having a composition of compositional formula (2):
D
0.5Eu
yLn
(1-y)M
2O
8 (2)
wherein D is at least one element selected from the group consisting of Mg,
Ca, Sr and Ba; Ln is at least one element selected from the group consisting of
Y and rare earth elements exclusive of Eu; M is at least one element selected from
the group consisting of W and Mo; and y is a positive number satisfying 0<y≦1,
preferably 0.3≦y≦1, most preferably 0.5≦y≦1.
In compositional formula (2), Ln is at least one element selected from the group
consisting of Y and rare earth elements exclusive of Eu, while Y, La, Gd and Lu
are preferred. D is preferably at least one element selected from Ca and Sr having
an ionic radius close to that of Eu.
The red light emitting phosphor of compositional formula (2) can be prepared
by mixing raw materials containing elements constituting the red light emitting
phosphor, firing the resulting mixture, optionally grinding and sieving the fired
product. The fired product is preferably washed with an aqueous acid solution because
the resulting red light emitting phosphor is capable of emitting red light of a
higher luminance. Examples of the aqueous acid solution used herein include an
aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, and an aqueous
nitric acid solution, with the pH being preferably 6 or lower. Washing with an
aqueous acid solution can be carried out by immersing the fired product in an aqueous
acid solution, optionally followed by agitation. Once washed with the aqueous acid
solution, the fired product is separated from the aqueous acid solution, washed
with water and dried, yielding a red light emitting phosphor.
[Red Light Emitting Phosphor]
In the red light emitting phosphor of the invention, Eu constituting the red
light
emitting phosphor is preferably in the form of trivalent europium ions (Eu
3+)
and especially, trivalent europium ions are arranged in a two- or one-dimensional
array. The arrangement of trivalent europium ions in a two-dimensional array refers
to the state in which trivalent europium ions in the red light emitting phosphor
are arranged in a plane, as shown in FIG. 1, forming a planar structure consisting
of trivalent europium ions. The arrangement of trivalent europium ions in a one-dimensional
array refers to the state in which trivalent europium ions in the red light emitting
phosphor are arranged in straight lines, as shown in FIG. 2, forming a linear structure
consisting of trivalent europium ions.
In oxide base phosphors, host crystals absorb excitation light and conduct the
excitation energy to emissive ions to produce light. Ordinary oxide base phosphors
provide insufficient absorption of long-wavelength ultraviolet radiation to short-wavelength
visible light (350 to 420 nm) because the wavelength corresponding to the excitation
energy of their electron pairs is in the ultraviolet region.
In ordinary phosphors, the concentration of emissive ions (activator) is several
molar percents relative to the host crystals. As is well known, concentration quenching
occurs at concentrations above that level for the reasons that (1) cross relaxation
occurs between activators due to resonant transfer whereby part of the excitation
energy is lost, (2) migration of excitation occurs due to resonant transfer between
activators, which promotes the transfer of excitation to the crystal surface or
non-luminescence center and annihilation, and (3) activators convert to non-luminescence
centers or killers (luminescence inhibitors) by agglomerating together or forming
ion pairs.
On the other hand, in the phosphor in which trivalent europium ions are arranged
in a two- or one-dimensional array, trivalent europium ions (Eu
3+) absorb
the excitation radiation and act as the luminescence center, and the trivalent
europium ions which are emissive ions directly absorb the long-wavelength ultraviolet
radiation to short-wavelength visible light (350 to 420 nm). Furthermore, since
there is a large spacing between layers where emissive ions are arranged, the migration
of the excitation energy is controlled, prohibiting concentration quenching. For
this reason, odd electrons within the 4f orbit of trivalent europium ions efficiently
absorb the long-wavelength ultraviolet radiation to short-wavelength visible light
(350 to 420 nm), producing red light emission at a high luminance.
[First Embodiment of Light Emitting Device]
The first embodiment of the light emitting device according to the invention
is described. The first embodiment is a light emitting device comprising a semiconductor
light emitter capable of emitting light having a wavelength of 350 to 420 nm, enclosed
in an encapsulant, wherein the inventive red light emitting phosphor described
above is dispersed in the encapsulant.
Illustrative embodiments include a so-called bullet-shaped light emitting
diode of the structure wherein leads
1 and
2, a semiconductor light
emitter
3 capable of emitting light having a wavelength of 350 to 420 nm,
and a lead thin wire
4 electrically connecting the semiconductor light emitter
3 to the lead
2 are enclosed in an encapsulant
5 of a bullet
shape, as shown in FIG. 3; and a so-called chip type light emitting diode of the
structure wherein a pair of leads
1 and
2 extend from the inner bottom
of an emitter casing
6 of box shape having an open top to the outside of
the casing
6, a semiconductor light emitter
3 capable of emitting
light having a wavelength of 350 to 420 nm and lead thin wires
4,
4
are accommodated within the casing
6, these components are connected, and
the interior of the casing
6 is filled with an encapsulant
5, as
shown in FIG.
4. The red light emitting phosphor of the invention is dispersed
in the encapsulant
5.
In these embodiments, when the red light-emitting phosphor of the invention is
dispersed alone in the encapsulant
5, the resulting light emitting device
emits red light at a high luminance. When the red light-emitting phosphor of the
invention is dispersed in the encapsulant
5 along with a green light-emitting
phosphor such as BaMg
2Al
16O
27:Eu,Mn, Zn
2GeO
4:Mn
or the like, and a blue light-emitting phosphor such as BaMg
2Al
16O
27:Eu,
(Sr,Ca,Ba)
5(PO
4)
3Cl:Eu or the like, the resulting
light emitting device emits white or intermediate color light at a high luminance.
In any of these light emitting devices, it is possible to add a red light-emitting
phosphor other than the inventive red light-emitting phosphor, such as Y
2O
2S:Eu,
La
2O
2S:Eu, 3.5MgO·0.5MgF
2·GeO
2:Mn
or the like as the red light-emitting phosphor.
The light emitting device illustrated above can be fabricated by encapsulating
a semiconductor light emitter or the like with an encapsulant material based on
a resin, rubber, elastomer, glass or the like while admixing the phosphor with
the encapsulant material. Particularly when two or more phosphors are used, the
red light-emitting phosphor of the invention, which has a higher true specific
gravity than conventional phosphors, can settle down faster than the other phosphor(s)
when admixed with the encapsulant material, with the risk of inducing color variations.
For this reason, the red light-emitting phosphor of the invention is preferably
dispersed in an encapsulant material by mixing it with a high viscosity material
such as a silicone rubber composition or silicone resin composition whose viscosity
has been adjusted using a thixotropy regulating agent, followed by curing. Besides
the above-mentioned phosphors, pigments, dyes, pseudo-pigments or the like may
also be added to the encapsulant material as a tone converting material.
[Second Embodiment of Light Emitting Device]
The second embodiment of the light emitting device according to the invention
is described. The second embodiment is a light emitting device comprising a semiconductor
light emitter capable of emitting light having a wavelength of 350 to 420 nm, enclosed
in an encapsulant, wherein a fluorescent layer containing the red light emitting
phosphor described above is disposed in an optical path of the light from the semiconductor
light emitter.
Exemplary of such devices are embodiments wherein a fluorescent layer containing
the red light emitting phosphor of the invention is disposed on the semiconductor
light emitter or the encapsulant. Illustrative embodiments include a so-called
bullet-shaped light emitting diode of the structure wherein leads
1 and
2, a semiconductor light emitter
3 capable of emitting light having
a wavelength of 350 to 420 nm, and a lead thin wire
4 electrically connecting
the semiconductor light emitter
3 to the lead
2 are enclosed in an
encapsulant
5 of a bullet shape, as shown in FIG. 5, and wherein a fluorescent
layer
7 is disposed on the semiconductor light emitter
3 and encapsulated
together with the semiconductor light emitter
3 and other components; a
so-called chip type light emitting diode of the structure wherein a pair of leads
1 and
2 extend from the inner bottom of an emitter casing
6
of box shape having an open top to the outside of the casing
6, a semiconductor
light emitter
3 capable of emitting light having a wavelength of 350 to
420 nm and lead thin wires
4,
4 are accommodated within the casing
6, these components are connected, and the interior of the casing
6
is filled with an encapsulant
5, as shown in FIG. 6, and wherein a fluorescent
layer
7 is disposed on the semiconductor light emitter
3 of the chip
type light emitting diode and encapsulated with the encapsulant
5 together
with the semiconductor light emitter
3 and other components; a bullet-shaped
light emitting diode as shown in FIG. 7 wherein a fluorescent layer
7 is
disposed on the encapsulant
5 so as to cover the encapsulant
5; and
a chip type light emitting diode as shown in FIG. 8 wherein a fluorescent layer
7 lies on the encapsulant
5. It is noted that since the components
other than the fluorescent layer in FIGS. 7 and 8 are the same as the corresponding
components in FIGS. 3 and 4, their description is omitted.
The inventive device is not limited to the embodiments of the so-called transmission
type wherein a fluorescent layer is disposed within or adjacent to a light emitting
diode as described above, and can also be embodied as a light emitting device of
the reflection type comprising a fluorescent layer
7 spaced apart from light
emitting diodes
8 and a reflector
9 wherein the reflector
9
reflects the light emitted by the fluorescent layer as shown in FIG.
9.
In the light emitting device having a fluorescent layer lying on the encapsulant
as shown in FIGS. 7 and 8, the fluorescent layer may be further covered with an encapsulant.
In these embodiments, when the red light-emitting phosphor of the invention is
dispersed alone in the fluorescent layer, the resulting light emitting device emits
red light at a high luminance. When the red light-emitting phosphor of the invention
is dispersed along with a green light-emitting phosphor such as BaMg
2Al
16O
27:Eu,Mn,
Zn
2GeO
4:Mn or the like, and a blue light-emitting phosphor
such as BaMg
2Al
16O
27:Eu, (Sr,Ca,Ba)
5(PO
4)
3Cl:Eu
or the like, the resulting light emitting device emits white or intermediate color
light at a high luminance. In any of these light emitting devices, it is possible
to add a red light-emitting phosphor other than the inventive red light-emitting
phosphor, such as Y
2O
2S:Eu, La
2O
2S:Eu,
3.5MgO·0.5MgF
2·GeO
2:Mn or the like as the red light-emitting phosphor.
Where the fluorescent layer is disposed on the semiconductor light emitter,
the phosphor may be used alone or in admixture with a binder. In this case, the
fluorescent layer is enclosed in the encapsulant together with the semiconductor
light emitter as shown in FIGS. 5 and 6.
On the other hand, where the fluorescent layer is disposed on the encapsulant,
the red light emitting phosphor is preferably used as a dispersion in a light transmissive
resin, rubber, elastomer or glass, especially a silicone resin or silicone rubber.
Particularly when two or more phosphors are dispersed in the fluorescent layer,
the inventive red light-emitting phosphor is preferably dispersed in the fluorescent
layer by mixing it with a silicone rubber composition or silicone resin composition
whose viscosity has been adjusted using a thixotropy regulating agent, followed
by curing, as in the aforementioned embodiment where the inventive red light-emitting
phosphor is dispersed in the encapsulant. The fluorescent layer may be a single
layer formed of a mixture of phosphors or a laminate consisting of layers of individual
phosphors. Besides the above-mentioned phosphors, pigments, dyes, pseudo-pigments
or the like may also be added to the fluorescent layer as a tone converting material.
EXAMPLE
Examples are given below for illustrating the present invention, but are
not construed as limiting the invention thereto.
Example 1
As phosphor-forming raw materials, 46.37 g of WO
3 powder, 17.60 g
of
Eu
2O
3 powder and 3.69 g of Li
2CO
3 powder
were weighed and uniformly mixed in a ball mill, giving a raw material mixture.
The raw material mixture was then placed in an alumina crucible where it was
fired at a temperature of 900° C. for 6 hours. The fired product was thoroughly
washed with pure water to remove the unnecessary soluble components, thereafter
finely milled in a ball mill, and sieved (sieve opening 53 μm), yielding
a red light emitting phosphor of the composition: LiEuW
2O
8.
For this red light emitting phosphor LiEuW
2O
8, the intensity
of emission upon excitation at 380 nm was determined by means of a compact spectrofluorometer
FP-750 (Nihon Bunko Co., Ltd.) using a conventional Y
2O
2S:Eu
phosphor as standard. A high value of 2.5 times the standard was recorded as shown
in FIG. 10. Since the emission of LiEuW
2O
8 has a peak
at 614 nm and the emission of Y
2O
2S:Eu has a peak at 624
nm, the combined use of these phosphors can increase the emission area of the red region.
Since the excitation wavelength of the red light emitting phosphor LiEuW
2O
8
is positioned in the range between long-wavelength ultraviolet and short-wavelength
visible light (350-420 nm), the light of wavelength within this range can be converted
to light of 614 nm. In particular, since maximum absorption peaks attributable
to the 4f—4f transition of Eu
3+ develop at 380 nm and 395 nm as
shown in FIG. 11, this phosphor is effective with an excitation light source of
emitting light having a wavelength of approximately 380 nm to 420 nm. Such a sharp
excitation wavelength proves that these are absorption peaks due to Eu
3+.
Examples 2-4
WO
3 powder, Eu
2O
3 powder, Li
2CO
3
powder and Y
2O
3 powder were weighed in such a stoichiometric
ratio that the ratio of metal elements and rare earth elements in the resultant
phosphor might be represented by LiEu
xY
(1-x)W
2O
8
wherein x=0.3, 0.5 or 0.7, and uniformly mixed in a ball mill, giving raw
material mixtures.
The raw material mixtures were then placed in an alumina crucible where they
were fired at a temperature of 900° C. for 6 hours. The fired products were
thoroughly washed with pure water to remove the unnecessary soluble components,
thereafter finely milled in a ball mill, and sieved (sieve opening 53 μm),
yielding red light emitting phosphors of the composition: LiEu
xY
(1-x)W
2O
8
wherein x=0.3, 0.5 and 0.7.
For these red light emitting phosphors, the intensity of emission upon excitation
at 380 nm was determined by means of the compact spectrofluorometer FP-750 (Nihon
Bunko Co., Ltd.) using the conventional Y
2O
2S:Eu phosphor
as standard. LiEu
xY
(1-x)W
2O
8 wherein
x=0.3 (Example 2) marked a high value of 1.4 times the standard, LiEu
xY
(1-x)W
2O
8
wherein x=0.5 (Example 3) marked a high value of 1.8 times the standard,
and LiEu
xY
(1-x)W
2O
8 wherein x=0.7 (Example
4) marked a high value of 2.2 times the standard.
Example 5
As phosphor-forming raw materials, 46.37 g of WO
3 powder, 17.60 g
of
Eu
2O
3 powder and 3.69 g of Li
2CO
3 powder
were weighed and uniformly mixed in a ball mill, giving a raw material mixture.
The raw material mixture was then placed in an alumina crucible where it was
fired at a temperature of 900° C. for 6 hours. The fired product was thoroughly
washed with pure water to remove the unnecessary soluble components, thereafter
finely milled in a ball mill, sieved (sieve opening 53 μm), and subjected
to aqueous alkali solution-washing treatment by immersing in a 2% sodium hydroxide
aqueous solution for 30 minutes. This was followed by water washing, filtration
and drying, yielding a red light emitting phosphor of the composition: LiEuW
2O
8.
For this red light emitting phosphor LiEuW
2O
8, the intensity
of emission upon excitation at 380 nm was determined by means of the compact spectrofluorometer
FP-750 (Nihon Bunko Co., Ltd.) using the conventional Y
2O
2S:Eu
phosphor as standard. It exhibited a relative emission intensity as high as 120.1,
provided that the emission intensity of the sample not subjected to aqueous alkali
solution-washing treatment was 100.
Examples 6-8
By following the procedure of Example 5 except that a lithium hydroxide aqueous
solution at pH 11 (Example 6), a sodium hydroxide aqueous solution at pH 11 (Example
7), or a potassium hydroxide aqueous solution at pH 11 (Example 8) was used instead
of the 2% sodium hydroxide aqueous solution, red light emitting phosphors of the
composition: LiEuW
2O
8 were obtained.
For these red light emitting phosphors LiEuW
2O
8, the intensity
of emission upon excitation at 380 nm was determined by means of the compact spectrofluorometer
FP-750 (Nihon Bunko Co., Ltd.) using the conventional Y
2O
2S:Eu
phosphor as standard. They exhibited a relative emission intensity as high as 101.0
(Example 6), 103.3 (Example 7) and 108.4 (Example 8), provided that the emission
intensity of the sample not subjected to aqueous alkali solution-washing treatment
was 100.
Example 9
As phosphor-forming raw materials, 46.37 g of WO
3 powder, 17.60 g
of
Eu
2O
3 powder and 5.00 g of CaCO
3 powder were weighed
and uniformly mixed in a ball mill, giving a raw material mixture.
The raw material mixture was then placed in an alumina crucible where it was
fired at a temperature of 900° C. for 6 hours. The fired product was thoroughly
washed with pure water to remove the unnecessary soluble components, thereafter
finely milled in a ball mill, sieved (sieve opening 53 μm), and subjected
to aqueous acid solution-washing treatment by immersing in a 2% hydrochloric acid
aqueous solution for 30 minutes. This was followed by water washing, filtration
and drying, yielding a red light emitting phosphor of the composition: Ca
0.5EuW
2O
8.
For this red light emitting phosphor Ca
0.5EuW
2O
8,
the intensity of emission upon excitation at 380 nm was determined by means of
the compact spectrofluorometer FP-750 (Nihon Bunko Co., Ltd.). It exhibited a relative
emission intensity as high as 117.5, provided that the emission intensity of the
sample not subjected to aqueous acid solution-washing treatment was 100.
Example 10
A fluorescent layer 7 in which LiEuW
2O
8 as a red light
emitting phosphor, Sr(PO
4)
3Cl:Eu as a blue light emitting
phosphor and BaMg
2Al
16O
27:Eu,Mn as a green light
emitting phosphor were mixed in a ratio of 10:3:3 and dispersed in silicone rubber
was shaped into a silicone rubber cap as shown in FIG. 7 by means of a heat press
machine. The cap as the fluorescent layer was fitted over an encapsulant of a ultraviolet
LED having an emission wavelength of 380 nm to construct a light emitting device
as shown in FIG. 7.
In an integrating sphere, a current flow of 20 mA was conducted across the light
emitting device for operation, and the spectral distribution of the light radiated
was determined by a spectroradiometer PR-704 (Photo Research Co.). The spectral
distribution is shown in FIG. 12. This light emitting device emitted white
light at a high luminance which was 2.3 times the luminance achieved using Y
2O
2S:Eu
as the red light emitting phosphor.
Example 11
A fluorescent layer 7 in which LiEuW
2O
8 and Y
2O
2S:Eu
as red light emitting phosphors, Sr
5(PO
4)
3Cl:Eu
as a blue light emitting phosphor and BaMg
2Al
16O
27:Eu,Mn
as a green light emitting phosphor were mixed in a ratio of 15:15:3:3 and dispersed
in silicone rubber was shaped into a silicone rubber cap as shown in FIG. 7 by
means of a heat press machine. The cap as the fluorescent layer was fitted over
an encapsulant of a ultraviolet LED having an emission wavelength of 380 nm to
construct a light emitting device as shown in FIG. 7.
In an integrating sphere, a current flow of 20 mA was conducted across the light
emitting device for operation, and the spectral distribution of the light radiated
was determined by the spectroradiometer PR-704 (Photo Research Co.). The spectral
distribution is shown in FIG. 13. This light emitting device emitted white
light at a high luminance which was 1.6 times the luminance achieved using Y
2O
2S:Eu
alone as the red light emitting phosphor.
As is evident from the foregoing, the red light emitting phosphor of the invention
emits red light at a high efficiency and a high luminance in response to excitation
light having a wavelength of 350 to 420 nm, is effective for drastically improving
the emission luminance in the red region of a light emitting device comprising
the red light emitting phosphor, and thus produces red emission at a consistent
intensity in response to a wide wavelength range of from long-wavelength ultraviolet
radiation to short-wavelength visible light.
Since the inventive red light emitting phosphor is little affected by variations
in wavelength of the exciting light, it enables to display a subtle color tone
in a more precise and reproducible manner when it is combined with green and blue
light emitting phosphors so that the phosphors produce emissions in response to
light from a semiconductor light emitter capable of emitting light of the above-described
wavelength, for providing a display of white or intermediate color.
*
