U.S. patent application number 12/854001 was filed with the patent office on 2010-12-02 for light emitting device.
This patent application is currently assigned to Seoul Semiconductor Co., Ltd.. Invention is credited to Chung-Hoon Lee, Gundula ROTH, Walter Tews.
Application Number | 20100301371 12/854001 |
Document ID | / |
Family ID | 34930126 |
Filed Date | 2010-12-02 |
United States Patent
Application |
20100301371 |
Kind Code |
A1 |
ROTH; Gundula ; et
al. |
December 2, 2010 |
LIGHT EMITTING DEVICE
Abstract
A light emitting device can be characterized as including a
light emitting diode configured to emit light and a phosphor
configured to change a wavelength of the light. The phosphor
substantially covers at least a portion of the light emitting
diode. The phosphor includes a compound having a host material.
Divalent copper ions and oxygen are components of the host
material.
Inventors: |
ROTH; Gundula; (Levenhagen,
DE) ; Tews; Walter; (Greifswald, DE) ; Lee;
Chung-Hoon; (Ansan-si, KR) |
Correspondence
Address: |
H.C. PARK & ASSOCIATES, PLC
8500 LEESBURG PIKE, SUITE 7500
VIENNA
VA
22182
US
|
Assignee: |
Seoul Semiconductor Co.,
Ltd.
Seoul
KR
|
Family ID: |
34930126 |
Appl. No.: |
12/854001 |
Filed: |
August 10, 2010 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
12098263 |
Apr 4, 2008 |
|
|
|
12854001 |
|
|
|
|
11024702 |
Dec 30, 2004 |
7554129 |
|
|
12098263 |
|
|
|
|
Current U.S.
Class: |
257/98 ;
257/E33.061 |
Current CPC
Class: |
C09K 11/7751 20130101;
C09K 11/666 20130101; C09K 11/7739 20130101; H01L 2924/00014
20130101; C09K 11/7796 20130101; C09K 11/7756 20130101; C09K
11/7734 20130101; H01L 33/502 20130101; C09K 11/665 20130101; C09K
11/774 20130101; C09K 11/753 20130101; C09K 11/7792 20130101; C09K
11/756 20130101; H01L 2224/48091 20130101; C09K 11/7735 20130101;
C09K 11/7738 20130101; H01L 2224/48247 20130101; H01L 2224/73265
20130101; H01L 2224/48091 20130101 |
Class at
Publication: |
257/98 ;
257/E33.061 |
International
Class: |
H01L 33/58 20100101
H01L033/58 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 10, 2004 |
KR |
2004-042396 |
Claims
1. A light emitting device, comprising: a light emitting diode
configured to emit light; and a phosphor configured to change a
wavelength of the light emitted from the light emitting diode, the
phosphor covering at least a portion of the light emitting diode;
wherein said phosphor comprises a compound including a host
material and an activator, and wherein divalent copper ions and
oxygen are components of the host material.
2. The light emitting device according to claim 1, wherein the
compound has the formula
a(M'O)b(M''.sub.2O)c(M''X)d(Al.sub.2O.sub.3)e(M'''O)f(M''''.sub.2O.sub.3)-
g(M'''''.sub.oO.sub.p)h(M''''''.sub.xO.sub.y) wherein M' is Cu, or
a combination of Cu and Pb; M'' is Li, Na, K, Rb, Cs, Au, Ag or any
combination thereof; M''' is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn or any
combination thereof; M''' is Sc, B, Ga, In, or any combination
thereof; M''''' is Si, Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, or any
combination thereof; M'''''' is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd,
Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or any combination
thereof; X is F, Cl, Br, I, or any combination thereof;
0<a.ltoreq.2; 0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.2;
0<d.ltoreq.8; 0<e.ltoreq.4; 0.ltoreq.f.ltoreq.3;
0.ltoreq.g.ltoreq.8; 0<h.ltoreq.2; 1<o<2;
1.ltoreq.p.ltoreq.5; 1.ltoreq.x.ltoreq.2; and
1.ltoreq.y.ltoreq.5.
3. The light emitting device according to claim 1, wherein the
compound has the formula
a(M'O)b(M''.sub.2O)c(M''X)4-a-b-c(M'''O)7(Al.sub.2O.sub.3)d(B.sub.2O.sub.-
3)e(Ga.sub.2O.sub.3)f(SiO.sub.2)g(GeO.sub.2)h(M''''.sub.xO.sub.y)
wherein M' is Cu, or a combination of Cu and Pb; M'' is Li, Na, K,
Rb, Cs, Au, Ag, or any combination thereof; M''' is Be, Mg, Ca, Sr,
Ba, Zn, Cd, Mn, or any combination thereof; M'''' is Bi, Sn, Sb,
Sc, Y, La, In, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
Lu, or any combination thereof; X is F, Cl, Br, I, or any
combination thereof; 0<a.ltoreq.4; 0<b.ltoreq.2;
0.ltoreq.c.ltoreq.2; 0.ltoreq.d.ltoreq.1; 0.ltoreq.e.ltoreq.1;
0.ltoreq.f.ltoreq.1; 0.ltoreq.g.ltoreq.1; 0<h.ltoreq.2;
1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
4. The light emitting device according to claim 1, wherein the
phosphor includes one or more single compounds or any combination
thereof.
5. The light emitting device according to claim 1, further
comprising a sealing material configured to cover the light
emitting diode and the phosphor.
6. The light emitting device according to claim 5, wherein the
phosphor is distributed in the sealing material.
7. The light emitting device according to claim 1, wherein the
phosphor is mixed with a hardening material.
8. The light emitting device according to claim 1, wherein the
light emitting diode comprises a plurality of light emitting
diodes.
9. The light emitting device according to claim 1, wherein the
phosphor comprises an aluminate containing copper, a silicate
containing copper, an antimonite containing copper, a germanate
containing copper, a germanate-silicate containing copper, a
phosphate containing copper, or any combination thereof.
10. The light emitting device according to claim 1, further
comprising: a substrate; a plurality of electrodes provided on the
substrate; and an electrically conductive device configured to
connect the light emitting diode with one of the plurality of
electrodes, wherein the light emitting diode is provided on another
of the plurality of electrodes.
11. The light emitting device according to claim 10, further
comprising electrically conductive paste provided between the light
emitting diode and one of the plurality of electrodes.
12. The light emitting device according to claim 10, further
comprising a reflector configured to reflect the light from the
light emitting diode.
13. The light emitting device according to claim 1, further
comprising: a plurality of leads; a diode holder provided at the
end of one of the plurality of leads; and an electrically
conductive device configured to connect the light emitting diode
with another of the plurality of leads, wherein the light emitting
diode is provided in the diode holder and includes a plurality of
electrodes.
14. The light emitting device according to claim 13, further
comprising electrically conductive paste provided between the light
emitting diode and one of the plurality of electrodes.
15. The light emitting device according to claim 1, further
comprising: a housing; a heat sink at least partially provided in
the housing; a plurality of lead frames provided on or around the
heat sink; and an electrically conductive device configured to
connect the light emitting diode with one of the plurality of lead
frames, wherein the light emitting diode is disposed over the heat
sink.
16. The light emitting device according to claim 15, further
comprising electrically conductive paste provided between the light
emitting diode and the heat sink.
17. The light emitting device according to claim 15, wherein at
least one of the plurality of lead frames protrudes from the
housing.
18. The light emitting device according to claim 15, wherein the
heat sink comprises a plurality of heat sinks.
19. The light emitting device according to claim 1, lead is a
component of the host material.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 12/098,263, filed Apr. 4, 2008, which is a
continuation of U.S. application Ser. No. 11/024,702, filed Dec.
30, 2004, now U.S. Pat. No. 7,554,129, and also claims priority of
Korean Patent Application No. 2004-042396, filed Jun. 10, 2004, the
contents of which are incorporated herein by reference in their
entirety.
FIELD OF THE INVENTION
[0002] The invention relates to light emitting devices and more
particularly to light emitting devices including at least one
light-emitting diode and phosphor, the phosphor including is lead
and/or copper doped chemical compounds and converting the
wavelength of light.
BACKGROUND OF THE INVENTION
[0003] Light emitting devices (LEDs), which used to be used for
electronic devices, are now used for automobiles and illumination
products. Since light emitting devices have superior electrical and
mechanical characteristics, demands for light emitting devices have
been increased. In connection to this, interests in white LEDs are
increasing as an alternative to fluorescent lamps and incandescent
lamps.
[0004] In LED technology, solution for realization of white light
is proposed variously. Normally, realization of white LED
technology is to put the phosphor on the light-emitting diode, and
mix the primary emission from the light emitting diode and the
secondary emission from the phosphor, which converts the
wavelength. For example, as shown in WO 98/05078 and WO 98/12757,
use a blue light emitting diode, which is capable of emitting a
peak wavelength at 450-490 nm, and YAG group material, which
absorbs light from the blue light emitting diode and emits
yellowish light (mostly), which may have different wavelength from
that of the absorbed light
[0005] However, in such a usual white LED, color temperature range
is narrow which is between about 6,000-8,000K, and CRI (Color
Rendering Index) is about 60 to 75. Therefore, it is hard to
produce the white LED with color coordination and color temperature
that are similar to those of the visible light. It is one of the
reasons why only white light color with a cold feeling could be
realized. Moreover, phosphors which are used for white LEDs are
usually unstable in the water, vapor or polar solvent, and this
unstableness may cause changes in the emitting characteristics of
white LED.
[0006] A light emitting device can be characterized as including a
light emitting diode configured to emit light and a phosphor
configured to change a wavelength of the light. The phosphor
includes a compound having a host material. Divalent copper ions
and oxygen are components of the host material.
DESCRIPTION OF THE DRAWINGS
[0007] Further aspects of the invention may be apparent upon
consideration of the following detailed description, taken in
conjunction with the accompanying drawings, in which like reference
characters refer to like parts throughout, and in which:
[0008] FIG. 1 shows a side cross-sectional view of an illustrative
embodiment of a portion of a chip-type package light emitting
device consistent with this invention;
[0009] FIG. 2 shows a side cross-sectional view of an illustrative
embodiment of a portion of a top-type package light emitting device
consistent with this invention;
[0010] FIG. 3 shows a side cross-sectional view of an illustrative
embodiment of a portion of a lamp-type package light emitting
device consistent with this invention;
[0011] FIG. 4 shows a side cross-sectional view of an illustrative
embodiment of a portion of a light emitting device for high power
consistent with this invention;
[0012] FIG. 5 shows a side cross-sectional view of another
illustrative embodiment of a portion of a light emitting device for
high power consistent with this invention;
[0013] FIG. 6 shows emitting spectrum of a light emitting device
with luminescent material consistent with this invention; and
[0014] FIG. 7 shows emitting spectrum of the light emitting device
with luminescent material according to another embodiment of the
invention.
DETAILED DESCRIPTION
[0015] Refer to the attached drawing, the wavelength conversion
light emitting device is going to be explained in detail, and the
light emitting device and the phosphor are separately is explained
for easiness of explanation as below.
[0016] (Light Emitting Device)
[0017] FIG. 1 shows a side cross-sectional view of an illustrative
embodiment of a portion of a chip-type package light emitting
device consistent with this invention. The chip-type package light
emitting device may comprise at least one light emitting diode and
a phosphorescent substance. Electrodes 5 may be formed on both
sides of substrate 1. Light emitting diode 6 emitting light may be
mounted on one of the electrodes 5. Light emitting diode 6 may be
mounted on electrode 5 through electrically conductive paste 9. An
electrode of light emitting diode 6 may be connected to electrode
pattern 5 via an electrically conductive wire 2.
[0018] Light emitting diodes may emit light with a wide range of
wavelengths, for example, from ultraviolet light to visible light.
In one embodiment consistent with this invention, a UV light
emitting diode and/or blue light emitting diode may be use.
[0019] Phosphor, i.e., a phosphorescent substance, 3 may be placed
on the top and side faces of the light emitting diode 6. The
phosphor in consistent with this invention may include lead and/or
copper doped aluminate type compounds, lead and/or copper doped
silicates, lead and/or copper doped antimonates, lead and/or copper
doped germanates, lead and/or copper doped germanate-silicates,
lead and/or copper doped phosphates, or any combination thereof.
Phosphor 3 converts the wavelength of the light from the light
emitting diode 6 to another wavelength or other wavelengths. In one
embodiment consistent with this invention, the light is in a
visible light range after the conversion. Phosphor 3 may be applied
to light emitting diode 6 after mixing phosphor 3 with a hardening
resin. The hardening resin including phosphor 3 may also be applied
to the bottom of light emitting diode 6 after mixing phosphor 3
with electrically conductive paste 9.
[0020] The light emitting diode 6 mounted on substrate 1 may be
sealed with one or more sealing materials 10. Phosphor 3 may be
placed on the top and side faces of light emitting is diode 6.
Phosphor 3 can also be distributed in the hardened sealing material
during the production. Such a manufacturing method is described in
U.S. Pat. No. 6,482,664, which is hereby incorporated by reference
in its entirety.
[0021] Phosphor 3 may comprise lead and/or copper doped chemical
compound(s). Phosphor 3 may include one or more single chemical
compounds. The single compound may have an emission peak of, for
example, from about 440 nm to about 500 nm, from about 500 nm to
about 590 nm, or from about 580 nm to 700 nm. Phosphor 3 may
include one or more single phosphors, which may have an emission
peak as exemplified above.
[0022] In regard to light emitting device 40, light emitting diode
6 may emit primary light when light emitting diode 6 receives power
from a power supply. The primary light then may stimulate
phosphor(s) 3, and phosphor(s) 3 may convert the primary light to a
light with longer wavelength(s) (a secondary light). The primary
light from the light emitting diode 6 and the secondary light from
the phosphors 3 are diffused and mixed together so that a
predetermined color of light in visible spectrum may be emitted
from light emitting diode 6. In one embodiment consistent with this
invention, more than one light emitting diodes that have different
emission peaks can be mounted together. Moreover, if the mixture
ratio of phosphors is adjusted properly, specific color of light,
color temperature, and CRI can be provided.
[0023] As described above, if the light emitting diode 6 and the
compound included in phosphor 3 are properly controlled then
desired color temperature or specific color coordination can be
provided, especially, wide range of color temperature, for example,
from about 2,000K to about 8,000K or about 10,000K and/or color
rendering index of greater than about 90. Therefore, the light
emitting devices consistent with this invention may be used for
electronic devices such as home appliances, stereos,
telecommunication devices, and for interior/exterior is custom
displays. The light emitting devices consistent with this invention
may also be used for automobiles and illumination products because
they provide similar color temperatures and CRI to those of the
visible light.
[0024] FIG. 2 shows a side cross-sectional view of an illustrative
embodiment of a portion of a top-type package light emitting device
consistent with this invention. A top-type package light emitting
device consistent with this invention may have a similar structure
as that of the chip type package light emitting device 40 of FIG.
1. The top-type package device may have reflector 31 which may
reflect the light from the light emitting diode 6 to the desire
direction.
[0025] In top-type package light emitting device 50, more than one
light emitting diodes can be mounted. Each of such light emitting
diodes may have a different peak wavelength from that of others.
Phosphor 3 may comprise a plurality of single compounds with
different emission peak. The proportion of each of such plurality
of compounds may be regulated. Such a phosphor may be applied to
the light emitting diode and/or uniformly distributed in the
hardening material of the reflector 31. As explained more fully
below, the phosphor in consistent with this invention may include
lead and/or copper doped aluminate type compounds, lead and/or
copper doped silicates, lead and/or copper doped antimonates, lead
and/or copper doped germanates, lead and/or copper doped
germanate-silicates, lead and/or copper doped phosphates, or any
combination thereof.
[0026] In one embodiment consistent with this invention, the light
emitting device of the FIG. or FIG. 2 can include a metal
substrate, which may have good heat conductivity. Such a light
emitting device may easily dissipate the heat from the light
emitting diode. Therefore, light emitting devices for high power
may be manufactured. If a heat sink is provided beneath the is
metal substrate, the heat from the light emitting diode may be
dissipated more effectively.
[0027] FIG. 3 shows a side cross-sectional view of an illustrative
embodiment of a portion of a lamp-type package light emitting
device consistent with this invention. Lamp type light emitting
device 60 may have a pair of leads 51, 52, and a diode holder 53
may be formed at the end of one lead. Diode holder 53 may have a
shape of cup, and one or more light emitting diodes 6 may provided
in the diode holder 53. When a number of light emitting diodes are
provided in the diode holder 53, each of them may have a different
peak wavelength from that of others. An electrode of light emitting
diode 6 may be connected to lead 52 by, for example, electrically
conductive wire 2.
[0028] Regular volume of phosphor 3, which may be mixed in the
epoxy resin, may be provided in diode holder 53. As explained more
fully below, phosphor 3 may include lead and/or copper doped
components.
[0029] Moreover, the diode holder may include the light emitting
diode 6 and the phosphor 3 may be sealed with hardening material
such as epoxy resin or silicon resin.
[0030] In one embodiment consistent with this invention, the lamp
type package light emitting device may have more than one pair of
electrode pair leads.
[0031] FIG. 4 shows a side cross-sectional view of an illustrative
embodiment of a portion of a light emitting device for high power
consistent with this invention. Heat sink 71 may be provided inside
of housing 73 of the light emitting device for high power 70, and
it may be partially exposed to outside. A pair of lead frame 74 may
protrude from housing 73.
[0032] One or more light emitting diodes may be mounted one lead
frame 74, and an electrode of the light emitting diode 6 and
another lead frame 74 may be connected via electrically conductive
wire. Electrically conductive pate 9 may be provided between light
is emitting diode 6 and lead frame 74. The phosphor 3 may be placed
on top and side faces of light emitting diode 6.
[0033] FIG. 5 shows a side cross-sectional view of another
illustrative embodiment of a portion of a light emitting device for
high power consistent with this invention.
[0034] Light emitting device for high power 80 may have housing 63,
which may contain light emitting diodes 6, 7, phosphor 3 arranged
on the top and side faces of light emitting diodes 6, 7, one or
more heat sinks 61, 62, and one or more lead frames 64. The lead
frames 64 may receive power from a power supplier and may protrude
from housing 63.
[0035] In the light emitting devices for high power 70, 80 in the
FIGS. 4 and 5, the phosphor 3 can be added to the paste, which may
be provided between heat sink and light emitting devices. A lens
may be combined with housing 63, 73.
[0036] In a light emitting device for high power consistent with
this invention, one or more light emitting diodes can be used
selectively and the phosphor can be regulated depending on the
light emitting diode. As explained more fully below, the phosphor
may include lead and/or copper doped components.
[0037] A light emitting device for high power consistent with this
invention may have a radiator (not shown) and/or heat sink(s). Air
or a fan may be used to cool the radiator.
[0038] The light emitting devices consistent with this invention is
not limited to the structures described above, and the structures
can be modified depending on the characteristics of light emitting
diodes, phosphor, wavelength of light, and also applications.
Moreover, new part can be added to the structures.
[0039] An exemplary phosphor consistent with this invention is as
follows.
[0040] (Phosphor)
[0041] Phosphor in consistence with this invention may include lead
and/or copper doped chemical compounds. The phosphor may be excited
by UV and/or visible light, for example, blue light. The compound
may include Aluminate, Silicate, Antimonate, Germanate,
Germanate-silicate, or Phosphate type compounds.
[0042] Aluminate type compounds may comprise compounds having
formula (1), (2), and/or (5)
a(M'O).b(M''.sub.2O).c(M''X).dAl.sub.2O.sub.3e(M'''O).f(M''''.sub.2O.sub-
.3).g(M'''''.sub.oO.sub.p)h(M''''''.sub.xO.sub.y) (1)
[0043] wherein M' may be Pb, Cu, and/or any combination thereof;
M'' may be one or more monovalent elements, for example, Li, Na, K,
Rb, Cs, Au, Ag, and/or any combination thereof; M''' may be one or
more divalent elements, for example, Be, Mg, Ca, Sr, Ba, Zn, Cd,
Mn, and/or any combination thereof; M'''' may be one or more
trivalent elements, for example, Sc, B, Ga, In, and/or any
combination thereof; M''''' may be Si, Ge, Ti, Zr, Mn, V, Nb, Ta,
W, Mo, and/or any combination thereof; M'''''' may be Bi, Sn, Sb,
Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,
and/or any combination thereof; X may be F, Cl, Br, J, and/or any
combination thereof; 0<a.ltoreq.2; 0.ltoreq.b.ltoreq.2;
0.ltoreq.c.ltoreq.2; 0.ltoreq.d.ltoreq.8; 0<e.ltoreq.4;
0.ltoreq.f.ltoreq.3; 0.ltoreq.g.ltoreq.8; 0<h.ltoreq.2;
1.ltoreq.o.ltoreq.2; 1.ltoreq.p.ltoreq.5; 1.ltoreq.x.ltoreq.2; and
1.ltoreq.y.ltoreq.5.
a(M'O).b(M''.sub.2O).c(M''X)4-a-b-c(M'''O).7(Al.sub.2O.sub.3).d(B.sub.2O-
.sub.3).e(Ga.sub.2O.sub.3).f(SiO.sub.2).g(GeO.sub.2).h(M''''.sub.xO.sub.y)
(2)
[0044] wherein M' may be Pb, Cu, and/or any combination thereof;
M'' may be one or more monovalent elements, for example, Li, Na, K,
Rb, Cs, Au, Ag, and/or any combination thereof; M''' may be one or
more divalent elements, for example, Be, Mg, Ca, Sr, Ba, Zn, Cd,
Mn, and/or any combination thereof; M'''' may be Bi, Sn, Sb, Sc, Y,
La, In, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and
any combination thereof; X may be F, Cl, Br, J, and any combination
thereof; 0<a.ltoreq.4; 0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.2;
0.ltoreq.d.ltoreq.1; 0.ltoreq.e.ltoreq.1; 0.ltoreq.f.ltoreq.1;
0.ltoreq.g.ltoreq.1; 0<h.ltoreq.2; 1.ltoreq.x.ltoreq.2; and
1.ltoreq.y.ltoreq.5.
[0045] The preparation of copper as well as lead doped luminescent
materials may be a basic solid state reaction. Pure starting
materials without any impurities, e.g. iron, may be used. Any
starting material which may transfer into oxides via a heating
process may be used to form oxygen dominated phosphors.
[0046] Examples of Preparation:
[0047] Preparation of the luminescent material having formula
(3)
Cu.sub.0.02Sr.sub.3.98Al.sub.14O.sub.25:Eu (3)
[0048] Starting materials: CuO, SrCO.sub.3, Al(OH).sub.3,
Eu.sub.2O.sub.3, and/or any combination thereof.
[0049] The starting materials in the form of oxides, hydroxides,
and/or carbonates may be mixed in stoichiometric proportions
together with small amounts of flux, e.g., H.sub.3BO.sub.3. The
mixture may be fired in an alumina crucible in a first step at
about 1,200.degree. C. for about one hour. After milling the
pre-fired materials a second firing step at about 1,450.degree. C.
in a reduced atmosphere for about 4 hours may be followed. After
that the material may be milled, washed, dried and sieved. The
resulting luminescent material may have an emission maximum of
about 494 nm.
TABLE-US-00001 TABLE 1 copper doped Eu.sup.2+-activated aluminate
compared with Eu.sup.2+-activated aluminate without copper at about
400 nm excitation wavelength. Compound Copper doped compound
without copper Cu.sub.0.02Sr.sub.3.98Al.sub.14O.sub.25:Eu
Sr.sub.4Al.sub.14O.sub.25:Eu Luminous density (%) 103.1 100
Wavelength (nm) 494 493
[0050] Preparation of the luminescent material having formula
(4)
Pb.sub.0.5Sr.sub.3.95Al.sub.14O.sub.25:Eu (4)
[0051] Starting materials: PbO, SrCO.sub.3, Al.sub.2O.sub.3,
Eu.sub.2O.sub.3, and/or any combination thereof.
[0052] The starting materials in form of very pure oxides,
carbonates, or other components which may decompose thermically
into oxides, may be mixed in stoichiometric proportion together
with small amounts of flux, for example, H.sub.3BO.sub.3. The
mixture may be fired in an alumina crucible at about 1,200.degree.
C. for about one hour in the air. After milling the pre-fired
materials a second firing step at about 1,450.degree. C. in air for
about 2 hours and in a reduced atmosphere for about 2 hours may be
followed. Then the material may be milled, washed, dried, and
sieved. The resulting luminescent material may have an emission
maximum of from about 494.5 nm.
TABLE-US-00002 TABLE 2 lead doped Eu.sup.2+-activated aluminate
compared with Eu.sup.2+-activated aluminate without lead at about
400 nm excitation wavelength Lead doped compound Compound without
lead Pb.sub.0.05Sr.sub.3.95Al.sub.14O.sub.25:Eu
Sr.sub.4Al.sub.14O.sub.25:Eu Luminous density (%) 101.4 100
Wavelength (nm) 494.5 493
TABLE-US-00003 TABLE 3 optical properties of some copper and/or
lead doped aluminates excitable by long wave ultraviolet and/or by
visible light and their luminous density in % at 400 nm excitation
wavelength. Luminous density at 400 nm Peak wave Peak wave
excitation length of length of Possible compared with lead/copper
materials excitation copper/lead not doped without range doped
materials lead/copper Composition (nm) compounds (%) (nm) (nm)
Cu.sub.0.5Sr.sub.3.5Al.sub.14O.sub.25:Eu 360-430 101.2 495 493
Cu.sub.0.02Sr.sub.3.98Al.sub.14O.sub.25:Eu 360-430 101.4 494.5 493
Pb.sub.0.05Sr.sub.3.95Al.sub.14O.sub.25:Eu 360-430 103. 494.5 493
Cu.sub.0.01Sr.sub.3.99Al.sub.13.995Si.sub.0.005O.sub.25:Eu 360-430
103 494 492
Cu.sub.0.01Sr.sub.3.395Ba.sub.0.595Al.sub.14O.sub.25:Eu, Dy 360-430
100.8 494 493
Pb.sub.0.05Sr.sub.3.95Al.sub.13.95Ga.sub.0.05O.sub.25:Eu 360-430
101.5 494 494
a(M'O).b(M''O).c(Al.sub.2O.sub.3).d(M'''.sub.2O.sub.3).e(M''''O.sub.2).f-
(M'''''-.sub.xO.sub.y) (5)
[0053] wherein M' may be Pb, Cu, and/or any combination thereof;
M'' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination
thereof; M''' may be B, Ga, In, and/or any combination thereof;
M'''' may be Si, Ge, Ti, Zr, Hf, and/or any combination thereof;
M''''' may is be Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof;
0<a.ltoreq.1; 0.ltoreq.b.ltoreq.2; 0<c.ltoreq.8;
0.ltoreq.d.ltoreq.1; 0.ltoreq.e.ltoreq.1; 0<f.ltoreq.2;
1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
[0054] Example of Preparation:
[0055] Preparation of the luminescent material having formula
(6)
Cu.sub.0.05Sr.sub.0.95Al.sub.1.9997Si.sub.0.0003O.sub.4:Eu (6)
[0056] Starting materials: CuO, SrCO.sub.3, Al.sub.2O.sub.3,
SiO.sub.3, Eu.sub.2O.sub.3, and/or any combination thereof.
[0057] The starting materials in the form of, for example, pure
oxides and/or as carbonates may be mixed in stoichiometric
proportions together with small amounts of flux, for example,
AlF.sub.3. The mixture may be fired in an alumina crucible at about
1,250.degree. C. in a reduced atmosphere for about 3 hours. After
that the material may be milled, washed, dried and sieved. The
resulting luminescent material may have an emission maximum of
about 521.5 nm.
TABLE-US-00004 TABLE 4 copper doped Eu.sup.2+-activated aluminate
compared with Eu.sup.2+-activated aluminate without copper at about
400 nm excitation wavelength. Compound Copper doped compound
without copper
Cu.sub.0.05Sr.sub.0.95Al.sub.1.9997Si.sub.0.0003O.sub.4:Eu
SrAl.sub.2O.sub.4:Eu Luminous density (%) 106 100 Wavelength (nm)
521.5 519
[0058] Preparation of the luminescent material having formula
(7)
Cu.sub.0.12BaMg.sub.1.88Al.sub.16O.sub.27:Eu (7)
[0059] Starting materials: CuO, MgO, BaCO.sub.3, Al(OH).sub.3,
Eu.sub.2O.sub.3, and/or any combination thereof.
[0060] The starting materials in the form of, for example, pure
oxides, hydroxides, and/or carbonates may be mixed in
stoichiometric proportions together with small amounts of flux, for
example, AlF.sub.3. The mixture may be fired in an alumina crucible
at about 1,420.degree. C. in a reduced atmosphere for about 2
hours. After that the material may be milled, washed, dried, and
sieved. The resulting luminescent material may have an emission
maximum of about 452 nm.
TABLE-US-00005 TABLE 5 copper doped Eu.sup.2+-activated aluminate
compared with copper not doped Eu.sup.2+-activated aluminate at 400
nm excitation wavelength. Compound Copper doped compound without
copper Cu.sub.0.12BaMg.sub.1.88Al.sub.16O.sub.27:Eu
BaMg.sub.2Al.sub.16O.sub.27:Eu Luminous density (%) 101 100
Wavelength (nm) 452 450
[0061] Preparation of the luminescent material having formula (8)
(8)
Pb.sub.0.1Sr.sub.0.9Al.sub.2O.sub.4:Eu (8)
[0062] Starting materials: PbO, SrCO.sub.3, Al(OH).sub.3,
Eu.sub.2O.sub.3, and/or any combination thereof.
[0063] The starting materials in form of, for example, pure oxides,
hydroxides, and/or carbonates may be mixed in stoichiometric
proportions together with small amounts of flux, for example,
H.sub.3BO.sub.3. The mixture may be fired in an alumina crucible at
about 1,000.degree. C. for about 2 hours in the air. After milling
the pre-fired materials a second firing step at about 1,420.degree.
C. in the air for about 1 hour and in a reduced atmosphere for
about 2 hours may be followed. After that the material may be
milled, washed, dried and sieved. The resulting luminescent
material may have an emission maximum of about 521 nm.
TABLE-US-00006 TABLE 6 lead doped Eu.sup.2+-activated aluminate
compared with Eu.sup.2+-activated aluminate without lead at about
400 nm excitation wavelength. Lead doped compound Compound without
lead Pb.sub.0.1Sr.sub.0.9Al.sub.2O.sub.4:Eu SrAl.sub.2O.sub.4:Eu
Luminous density (%) 102 100 Wavelength (nm) 521 519
[0064] Results obtained in regard to copper and/or lead doped
aluminates are shown in table 7.
TABLE-US-00007 TABLE 7 optical properties of some copper and/or
lead doped aluminates excitable by long wave ultraviolet and/or by
visible light and their luminous density in % at 400 nm excitation
wavelength. Luminous density at 400 nm Peak wave Peak wave
excitation length of length of Possible compared with lead/copper
materials excitation copper/lead not doped without range doped
materials lead/copper Composition (nm) compounds (%) (nm) (nm)
Cu.sub.0.05Sr.sub.0.95Al.sub.1.9997Si.sub.0.0003O.sub.4:Eu 360-440
106 521.5 519
Cu.sub.0.2Mg.sub.0.7995Li.sub.0.0005Al.sub.1.9Ga.sub.0.1O.sub.4:Eu,
Dy 360-440 101.2 482 480 Pb.sub.0.1Sr.sub.0.09Al.sub.2O.sub.4:Eu
360-440 102 521 519 Cu.sub.0.05BaMg.sub.1.95Al.sub.16O.sub.27:Eu,
Mn 360-400 100.5 451, 515 450, 515
Cu.sub.0.12BaMg.sub.1.88Al.sub.16O.sub.27:Eu 360-400 101 452 449
Cu.sub.0.01BaMg.sub.0.99Al.sub.10O.sub.17:Eu 360-400 102.5 451 449
Cu.sub.0.01BaMg.sub.0.9Al.sub.9.5Ga.sub.0.5O.sub.17:Eu, Dy 360-400
100.8 448 450 Pb.sub.0.08Sr.sub.0.902Al.sub.2O.sub.4:Eu, Dy 360-440
102.4 521 519 Pb.sub.0.2Sr.sub.0.8Al.sub.2O.sub.4:Mn 360-440 100.8
658 655 Cu.sub.0.06Sr.sub.0.94Al.sub.2O.sub.4:Eu 360-440 102.3 521
519
Cu.sub.0.05Ba.sub.0.94Pb.sub.0.06Mg.sub.0.95Al.sub.10O.sub.17:Eu
360-440 100.4 451 449
Pb.sub.0.3Ba.sub.0.7Cu.sub.0.1Mg.sub.1.9Al.sub.16O.sub.27:Eu
360-400 100.8 452 450
Pb.sub.0.3Ba.sub.0.7Cu.sub.0.1Mg.sub.1.9Al.sub.16O.sub.27:Eu, Mn
360-400 100.4 452, 515 450, 515
[0065] A lead and/or copper doped silicates having formula (9)
a(M'O).b(M''O).c(M'''X).d(M'''.sub.2O).e(M''''.sub.2O.sub.3).f(M'''''.su-
b.oO.sub.p).g(SiO.sub.2).h(M''''''.sub.xO.sub.y) (9)
[0066] wherein M' may be Pb, Cu, and/or any combination thereof;
M'' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination
thereof; M''' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any
combination thereof; M'''' may be Al, Ga, In, and/or any
combination thereof; M''''' may be Ge, V, Nb, Ta, W, Mo, Ti, Zr,
Hf, and/or any combination thereof; M'''''' may be Bi, Sn, Sb, Sc,
Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,
and/or any combination thereof; X may be F, Cl, Br, J, and any
combination thereof; 0<a.ltoreq.2; 0<b.ltoreq.8;
0.ltoreq.c.ltoreq.4; 0.ltoreq.d.ltoreq.2; 0.ltoreq.e.ltoreq.2;
0.ltoreq.f.ltoreq.2; 0.ltoreq.g.ltoreq.10; 0<h.ltoreq.5;
1.ltoreq.o.ltoreq.2; 1.ltoreq.p.ltoreq.5; 1.ltoreq.x.ltoreq.2; and
1.ltoreq.y.ltoreq.5.
[0067] Example of Preparation:
[0068] Preparation of the luminescent material having formula
(10)
Cu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu (10)
[0069] Starting materials: CuO, SrCO.sub.3, CaCO.sub.3, SiO.sub.2,
Eu.sub.2O.sub.3, and/or any combination thereof.
[0070] The starting materials in the form of pure oxides and/or
carbonates may be mixed in stoichiometric proportions together with
small amounts of flux, for example, NH.sub.4Cl. The mixture may be
fired in an alumina crucible at about 1,200.degree. C. in an inert
gas atmosphere (e.g., N.sub.2 or noble gas) for about 2 hours. Then
the material may be milled. After that, the material may be fired
in an alumina crucible at about 1,200.degree. C. in a slightly
reduced atmosphere for about 2 hours. Then, the material may be
milled, washed, dried, and sieved. The resulting luminescent
material may have an emission maximum at about 592 nm.
TABLE-US-00008 TABLE 8 copper doped Eu.sup.2+-activated silicate
compared with Eu.sup.2+-activated silicate without copper at about
400 nm excitation wavelength. Copper doped compound Compound
without copper Cu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu
Si.sub.1.7Ca.sub.0.3SiO.sub.4:Eu Luminous 104 100 density (%)
Wavelength (nm) 592 588
[0071] Preparation of the Luminescent Material Having Formula
(11):
Cu.sub.0.2Ba.sub.2Zn.sub.0.2Mg.sub.0.6Si.sub.2O.sub.7:Eu (11)
[0072] Starting materials: CuO, BaCO.sub.3, ZnO, MgO, SiO.sub.2,
Eu.sub.2O.sub.3, and/or any combination thereof.
[0073] The starting materials in the form of very pure oxides and
carbonates may be mixed in stoichiometric proportions together with
small amounts of flux, for example, NH.sub.4Cl. In a first step the
mixture may be fired in an alumina crucible at about 1,100.degree.
C. in a reduced atmosphere for about 2 hours. Then the material may
be milled. After that the material may be fired in an alumina
crucible at about 1,235.degree. C. in a reduced atmosphere for
about 2 hours. Then that the material may be milled, washed, dried
and sieved. The resulting luminescent material may have an emission
maximum at about 467 nm.
TABLE-US-00009 TABLE 9 copper doped Eu.sup.2+-activated silicate
compared with Eu.sup.2+-activated silicate without copper at 400 nm
excitation wavelength. Compound Copper doped compound without
copper Cu.sub.0.2Sr.sub.2Zn.sub.0.2Mg.sub.0.6Si.sub.2O.sub.7:Eu
Sr.sub.2Zn.sub.2Mg.sub.0.6Si.sub.2O.sub.7:Eu Luminous 101.5 100
density (%) Wavelength (nm) 467 465
[0074] Preparation of the luminescent material having formula
(12)
Pb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu
(12)
[0075] Starting materials: PbO, SrCO.sub.3, BaCO.sub.3, SiO.sub.2,
GeO.sub.2, Eu.sub.2O.sub.3, and/or any combination thereof.
[0076] The starting materials in the form of oxides and/or
carbonates may be mixed in stoichiometric proportions together with
small amounts of flux, for example, NH.sub.4Cl. The mixture may be
fired in an alumina crucible at about 1,000.degree. C. for about 2
hours in the air. After milling the pre-fired materials a second
firing step at 1,220.degree. C. in air for 4 hours and in reducing
atmosphere for 2 hours may be followed. After that the material may
be milled, washed, dried and sieved. The resulting luminescent
material may have an emission maximum at about 527 nm.
TABLE-US-00010 TABLE 10 lead doped Eu.sup.2+-activated silicate
compared with Eu.sup.2+-activated silicate without lead at about
400 nm excitation wavelength. Compound Lead doped compound without
lead
Pb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu
BaSrSiO.sub.4:Eu Luminous 101.3 100 density (%) Wavelength (nm) 527
525
[0077] Preparation of the luminescent material having formula
(13)
Pb.sub.0.25Sr.sub.3.75Si.sub.3O.sub.8Cl.sub.4:Eu (13)
[0078] Starting materials: PbO, SrCO.sub.3, SrCl.sub.2, SiO.sub.2,
Eu.sub.2O.sub.3, and any combination thereof.
[0079] The starting materials in the form of oxides, chlorides,
and/or carbonates may be mixed in stoichiometric proportions
together with small amounts of flux, for example, NH.sub.4Cl. The
mixture may be fired in an alumina crucible in a first step at
about 1,100.degree. C. for about 2 hours in the air. After milling
the pre-fired materials a second firing step at about 1,220.degree.
C. in the air for about 4 hours and in a reduced atmosphere for
about 1 hour may be followed. After that the material may be
milled, washed, dried and sieved. The resulting luminescent
material may have an emission maximum at about 492 nm.
TABLE-US-00011 TABLE 11 lead doped Eu.sup.2+-activated
chlorosilicate compared with Eu.sup.2+-activated chlorosilicate
without lead at 400 nm excitation wavelength. Lead doped compound
Compound without lead
Pb.sub.0.25Sr.sub.3.75Si.sub.3O.sub.8Cl.sub.4:Eu
Sr.sub.4Si.sub.3O.sub.8Cl.sub.4:Eu Luminous 100.6 100 density (%)
Wavelength (nm) 492 490
[0080] Results obtained with respect to copper and/or lead doped
silicates are shown in table 12.
TABLE-US-00012 TABLE 12 optical properties of some copper and/or
lead doped rare earth activated silicates excitable by long wave
ultraviolet and/or by visible light and their luminous density in %
at about 400 nm excitation wavelength. Luminous density at 400 nm
Peak wave Peak wave excitation length of length of Possible
compared with lead/copper materials excitation copper/lead not
doped without range doped materials lead/copper Composition (nm)
compounds (%) (nm) (nm)
Pb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu
360-470 101.3 527 525 Cu.sub.0.02(Ba,Sr,Ca,Zn).sub.1.98SiO.sub.4:Eu
360-500 108.2 565 560 Cu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu
360-470 104 592 588
Cu.sub.0.05Li.sub.0.002Sr.sub.1.5Ba.sub.0.448SiO.sub.4:Gd, Eu
360-470 102.5 557 555
Cu.sub.0.2Sr.sub.1Zu.sub.0.2Mg.sub.0.5Si.sub.1O.sub.7:Eu 360-450
101.5 467 465
Cu.sub.0.02Ba.sub.2.8Sr.sub.0.2Mg.sub.0.98Si.sub.2O.sub.8:Eu, Mn
360-420 100.8 440, 660 438, 660
Pb.sub.0.25Sr.sub.3.75Si.sub.3O.sub.8Cl.sub.4:Eu 360-470 100.6 492
490
Cu.sub.0.2Ba.sub.2.2Sr.sub.0.75Pb.sub.0.05Zn.sub.0.8Si.sub.2O.sub.8:Eu
360-430 100.8 448 445
Cu.sub.0.2Ba.sub.3Mg.sub.0.8Si.sub.1.99Ge.sub.0.01O.sub.8:Eu
360-430 101 444 440
Cu.sub.0.5Zn.sub.0.5Ba.sub.2Ge.sub.0.2Si.sub.1.8O.sub.7:Eu 360-420
102.5 435 433 Cu.sub.0.8Mg.sub.0.2Ba.sub.3Si.sub.2O.sub.8:Eu, Mn
360-430 103 438, 670 435, 670
Pb.sub.0.15Ba.sub.1.84Zn.sub.0.01Si.sub.0.99Zr.sub.0.01O.sub.4:Eu
360-500 101 512 510 Cu.sub.0.2Ba.sub.5Ca.sub.2.8Si.sub.4O.sub.16:Eu
360-470 101.8 495 491
[0081] With lead and/or copper doped antimonates having formula
(14)
a(M'O).b(M''.sub.2O).c(M''X).d(Sb.sub.2O.sub.5).e(M'''O).f(M''''.sub.xO.-
sub.y) (14)
[0082] wherein M' may be Pb, Cu, and/or any combination thereof;
M'' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination
thereof; M''' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any
combination thereof; M'''' may be Bi, Sn, Sc, Y, La, Pr, Sm, Eu,
Tb, Dy, Gd, and/or any combination thereof; X may be F, Cl, Br, J,
and/or any combination thereof; 0<a.ltoreq.2;
0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.4; 0<d.ltoreq.8;
0.ltoreq.e.ltoreq.8; 0.ltoreq.f.ltoreq.2; 1.ltoreq.x.ltoreq.2; and
1.ltoreq.y.ltoreq.5.
[0083] Examples of Preparation:
[0084] Preparation of the luminescent material having formula
(15)
Cu.sub.0.2Mg.sub.1.7Li.sub.0.2Sb.sub.2O.sub.7:Mn (15)
[0085] Starting materials: CuO, MgO, Li.sub.2O, Sb.sub.2O.sub.5,
MnCO.sub.3, and/or any combination is thereof.
[0086] The starting materials in the form of oxides may be mixed in
stoichiometric proportion together with small amounts of flux. In a
first step the mixture may be fired in an alumina crucible at about
985.degree. C. in the air for about 2 hours. After pre-firing the
material may be milled again. In a second step the mixture may be
fired in an alumina crucible at about 1,200.degree. C. in an
atmosphere containing oxygen for about 8 hours. After that the
material may be milled, washed, dried and sieved. The resulting
luminescent material may have an emission maximum at about 626
nm.
TABLE-US-00013 TABLE 13 copper doped antimonate compared with
antimonate without copper at about 400 nm excitation wavelength.
Comparison Copper doped compound without copper
Cu.sub.0.2Mg.sub.1.7Li.sub.0.2Sb.sub.2O.sub.7:Mn
Mg.sub.2Li.sub.0.2Sb.sub.2O.sub.7:Mn Luminous density (%) 101.8 100
Wavelength (nm) 652 650
[0087] Preparation of the luminescent material having formula
(16)
Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.2O.sub.6 (16)
[0088] Starting materials: PbO, CaCO.sub.3, SrCO.sub.3,
Sb.sub.2O.sub.5, and/or any combination thereof.
[0089] The starting materials in the form of oxides and/or
carbonates may be mixed in stoichiometric proportions together with
small amounts of flux. In a first step the mixture may be fired in
an alumina crucible at about 975.degree. C. in the air for about 2
hours. After pre-firing the material may be milled again. In a
second step the mixture may be fired in an alumina crucible at
about 1,175.degree. C. in the air for about 4 hours and then in an
oxygen-containing atmosphere for about 4 hours. After that the
material may be milled, washed, dried and sieved. The resulting
luminescent material may have an emission maximum at about 637
nm.
TABLE-US-00014 TABLE 14 lead doped antimonate compared with
antimonate without lead at 400 nm excitation wavelength. Lead doped
compound Compound without lead
Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.0O.sub.6
Ca.sub.0.6Sr.sub.0.4Sb.sub.2O.sub.6 Luminous 102 100 density (%)
Wavelength (nm) 637 638
[0090] Results obtained in respect to copper and/or lead doped
antimonates are shown in table 15.
TABLE-US-00015 TABLE 15 optical properties of some copper and/or
lead doped antimonates excitable by long wave ultraviolet and/or by
visible light and their luminous density in % at about 400 nm
excitation wavelength. Luminous density at 400 nm Peak wave Peak
wave excitation length of length of Possible compared with
lead/copper materials excitation copper/lead not dope without range
doped compounds materials lead/copper Composition (nm) (%) (nm)
(nm) Pb.sub.0.2Mg.sub.0.002Ca.sub.1.798Sb.sub.2O.sub.6F.sub.2:Mn
360-400 102 645 649
Cu.sub.0.15Ca.sub.1.845Sr.sub.0.005Sb.sub.1.998Si.sub.0.002O.sub.7:Mn
360-400 101.5 660 658
Cu.sub.0.2Mg.sub.1.7Li.sub.0.2Sb.sub.2O.sub.7:Mn 360-400 101.8 652
650
Cu.sub.0.2Pb.sub.0.01Ca.sub.0.79Sb.sub.1.98Nb.sub.0.02O.sub.6:Mn
360-400 98.5 658 658
Cu.sub.0.01Ca.sub.1.99Sb.sub.1.9995V.sub.0.0005O.sub.7:Mn 360-400
100.5 660 657 Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.2O.sub.6
360-400 102 637 638
Cu.sub.0.02Ca.sub.0.9Sr.sub.0.5Ba.sub.0.4Mg.sub.0.18Sb.sub.2O.sub.7
360-400 102.5 649 645
Pb.sub.0.198Mg.sub.0.004Ca.sub.1.798Sb.sub.2O.sub.6F.sub.2 360-400
101.8 628 630
[0091] Lead and/or copper doped germanates and/or a
germanate-silicates having formula (17)
a(M'O).b(M''.sub.2O).c(M''X).dGeO.sub.2.e(M'''O).f(M''''.sub.2O.sub.3).g-
(M'''''.sub.oO.sub.p).h(M''''''.sub.xO.sub.y) (17)
[0092] wherein M' may be Pb, Cu, and/or any combination thereof;
M'' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination
thereof; M''' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, and/or any
combination thereof; M'''' may be Sc, Y, B, Al, La, Ga, In, and/or
any combination thereof; M''''' may be Si, Ti, Zr, Mn, V, Nb, Ta,
W, Mo, and/or any combination thereof; M'''''' may be Bi, Sn, Pr,
Sm, Eu, Gd, Dy, and/or any combination thereof; X may be F, Cl, Br,
J, and/or any combination thereof; 0<a.ltoreq.2;
0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.10; 0<d.ltoreq.10;
0.ltoreq.e.ltoreq.14; 0.ltoreq.f.ltoreq.14; 0.ltoreq.g.ltoreq.10;
0.ltoreq.h.ltoreq.2; 1.ltoreq.o.ltoreq.2; 1.ltoreq.p.ltoreq.5;
1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
[0093] Example of Preparation:
[0094] Preparation of the luminescent material having formula
(18)
Pb.sub.0.004Ca.sub.1.99Zn.sub.0.006Ge.sub.0.8Si.sub.0.2O.sub.4:Mn
(18)
[0095] Starting materials: PbO, CaCO.sub.3, ZnO, GeO.sub.2,
SiO.sub.2, MnCO.sub.3, and/or any combination thereof,
[0096] The starting materials in the form of oxides and/or
carbonates may be mixed in stoichiometric proportions together with
small amounts of flux, for example, NH.sub.4Cl. In a first step the
mixture may be fired in an alumina crucible at about 1,200.degree.
C. in an oxygen-containing atmosphere for about 2 hours. Then, the
material may be milled again. In a second step the mixture may be
fired in an alumina crucible at about 1,200.degree. C. in oxygen
containing atmosphere for about 2 hours. After that the material
may be milled, washed, dried and sieved. The resulting luminescent
material may have an emission maximum at about 655 nm.
TABLE-US-00016 TABLE 16 lead doped Mn-activated germanate compared
with Mn-activated germanate without lead at about 400 nm excitation
wavelength Copper doped compound Comparison without copper
Pb.sub.0.004Ca.sub.1.99Zn.sub.0.006Ge.sub.0.8Si.sub.0.2O.sub.4:Mn
Ca.sub.1.99Zn.sub.0.01Ge.sub.0.8Si.sub.0.2O.sub.4:Mn Luminous
density (%) 101.5 100 Wavelength (nm) 655 657
[0097] Preparation of the luminescent material having formula
(19)
Cu.sub.0.46Sr.sub.0.54Ge.sub.0.6Si.sub.0.4O.sub.3:Mn (19)
[0098] Starting materials: CuO, SrCO.sub.3, GeO.sub.2, SiO.sub.2,
MnCO.sub.3, and/or any combination thereof.
[0099] The starting materials in the form of oxides and/or
carbonates may be mixed in stoichiometric proportions together with
small amounts of flux, for example, NH.sub.4Cl. In a first step the
mixture may be fired in an alumina crucible at about 1,100.degree.
C. in an oxygen-containing atmosphere for about 2 hours. Then, the
material may be milled again. In a second step the mixture may be
fired in an alumina crucible at about 1,180.degree. C. in an
oxygen-containing atmosphere for about 4 hours. After that the
material may be milled, washed, dried and sieved. The resulting
luminescent material may have an emission maximum at about 658
nm.
TABLE-US-00017 TABLE 17 copper doped Mn-activated
germanate-silicate compared with Mn- activated germanate-silicate
without copper at 400 nm excitation wavelength Compound Copper
doped compound without copper
Cu.sub.0.46Sr.sub.0.54Ge.sub.0.6Si.sub.0.4O.sub.3:Mn
SrGe.sub.0.6Si.sub.0.4O.sub.3:Mn Luminous 103 100 density (%)
Wavelength (nm) 658 655
TABLE-US-00018 TABLE 18 optical properties of some copper and/or
lead doped germanate-silicates excitable by long wave ultraviolet
and/or by visible light and their luminous density in % at about
400 nm excitation wavelength Luminous density at 400 nm Peak wave
Peak wave excitation length of length of Possible compared with
lead/copper materials excitation copper/lead not doped without
range doped materials lead/copper Composition (nm) compounds (%)
(nm) (nm)
Pb.sub.0.004Ca.sub.1.99Zn.sub.0.006Ge.sub.0.8Si.sub.0.2O.sub.4:Mn
360-400 101.5 655 657
Pb.sub.0.002Sr.sub.0.954Ca.sub.1.044Ge.sub.0.93Si.sub.0.07O.sub.4:Mn
360-400 101.5 660 661
Cu.sub.0.46Sr.sub.0.54Ge.sub.0.6Si.sub.0.4O.sub.3:Mn 360-400 103
658 655
Cu.sub.0.002Sr.sub.0.998Ba.sub.0.99Ca.sub.0.01Si.sub.0.98Ge.sub.0.02O.sub.-
4:Eu 360-470 102 538 533
Cu.sub.1.45Mg.sub.26.55Ge.sub.9.4Si.sub.0.6O.sub.48:Mn 360-400 102
660 657 Cu.sub.1.2Mg.sub.26.8Ge.sub.8.9Si.sub.1.1O.sub.48:Mn
360-400 103.8 670 656
Cu.sub.4Mg.sub.20Zn.sub.4Ge.sub.5Si.sub.2.5O.sub.38F.sub.10:Mn
360-400 101.5 658 655
Pb.sub.0.001Ba.sub.0.849Zn.sub.0.05Sr.sub.1.1Ge.sub.0.04Si.sub.0.96O.sub.4-
:Eu 360-470 101.8 550 545 Cu.sub.0.05Mg.sub.4.95GeO.sub.6F.sub.2:Mn
360-400 100.5 655 653 Cu.sub.0.05Mg.sub.3.95GeO.sub.5.5F:Mn 360-400
100.8 657 653
[0100] Lead and/or copper doped phosphates having formula (20)
a(M'O).b(M''.sub.2O).c(M''X).dP.sub.2O.sub.5.e(M'''O).f(M''''.sub.2O.sub-
.3).g(M'''''O.sub.2).h(M''''''.sub.xO.sub.y) (20)
[0101] wherein M' may be Pb, Cu, and/or any combination thereof;
M'' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination
thereof; M''' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any
combination thereof; M'''' may be Sc, Y, B, Al, La, Ga, In, and/or
any combination thereof; M''''' may be Si, Ge, Ti, Zr, Hf, V, Nb,
Ta, W, Mo, and/or any combination thereof; M'''''' may be Bi, Sn,
Pr, Sm, Eu, Gd, Dy, Ce, Tb, and/or any combination thereof; X may
be F, Cl, Br, J, and/or any combination thereof; 0<a.ltoreq.2;
0.ltoreq.b.ltoreq.12; 0.ltoreq.c.ltoreq.16; 0<d.ltoreq.3;
0.ltoreq.e.ltoreq.5; 0.ltoreq.f.ltoreq.3; 0.ltoreq.g.ltoreq.2;
0<h.ltoreq.2; 1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
[0102] Examples of Preparation:
[0103] Preparation of the luminescent material having formula
(21)
Cu.sub.0.02Ca.sub.4.98(PO.sub.4).sub.3Cl:Eu (21)
[0104] Starting materials: CuO, CaCO.sub.3,
Ca.sub.3(PO.sub.4).sub.2, CaCl.sub.2, Eu.sub.2O.sub.3, and/or any
combination thereof.
[0105] The starting materials in the form of oxides, phosphates,
and/or carbonates and chlorides may be mixed in stoichiometric
proportions together with small amounts of flux. The mixture may be
fired in an alumina crucible at about 1,240.degree. C. in reducing
atmosphere for about 2 hours. After that the material may be
milled, washed, dried and sieved. The luminescent material may have
an emission maximum at about 450 nm.
TABLE-US-00019 TABLE 19 copper doped Eu.sup.2+-activated
chlorophosphate compared with Eu.sup.2+- activated chlorophosphate
without copper at about 400 nm excitation wavelength. Copper doped
compound Compound without copper Cu.sub.0.02Ca.sub.4.98
(PO.sub.4).sub.3Cl:Eu Ca.sub.5(PO.sub.4).sub.3Cl:Eu Luminous 101.5
100 density (%) Wavelength (nm) 450 447
TABLE-US-00020 TABLE 20 copper and/or lead doped phosphates
excitable by long wave ultraviolet and/or by visible light and
their luminous density in % at about 400 nm excitation wavelength
Luminous density at 400 nm Peak wave Peak wave excitation length of
length of Possible compared with lead/copper materials excitation
copper/lead not doped without range doped materials lead/copper
Composition (nm) compounds (%) (nm) (nm)
Cu.sub.0.02Sr.sub.4.98(PO.sub.4).sub.3Cl:Eu 360-410 101.5 450 447
Cu.sub.0.2Mg.sub.0.8BaP.sub.2O.sub.7:Eu 360-400 102 638 635
Pb.sub.0.5Sr.sub.1.5P.sub.1.84B.sub.0.16O.sub.6.84:Eu 360-400 102
425 420 Cu.sub.0.5Mg.sub.0.5Ba.sub.2(P,Si).sub.2O.sub.8:Eu 360-400
101 573 570 Cu.sub.0.5Sr.sub.9.5(P,B).sub.6O.sub.24Cl.sub.2:Eu
360-410 102 460 456
Cu.sub.0.5Ba.sub.3Sr.sub.6.5P.sub.6O.sub.24(F,Cl).sub.2:Eu 360-410
102 443 442 Cu.sub.0.05(Ca,Sr,Ba).sub.4.95P.sub.3O.sub.12Cl:Eu, Mn
360-410 101.5 438, 641 435, 640
Pb.sub.0.1Ba.sub.2.9P.sub.2O.sub.8:Eu 360-400 103 421 419
[0106] Meanwhile, the phosphor of the light emitting device
consistent with this invention can comprise aluminate, silicate,
antimonate, germanate, phosphate type chemical compound, and any
combination thereof.
[0107] FIG. 6 is a one of the embodiment's emission spectrum
according to the invention, which the phosphor is used for the
light emitting device. The embodiment may have a light emitting
diode with 405 nm wavelength and the phosphor, which is mixture of
the selected multiple chemical compounds in proper ratio. The
phosphor may be composed of
Cu.sub.0.05BaMg.sub.1.95Al.sub.16O.sub.27:Eu which may have peak
wavelength at about 451 nm,
Cu.sub.0.03Sr.sub.1.5Ca.sub.0.47SiO.sub.4:Eu which may have peak
wavelength at 586 nm,
Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.2O.sub.6:Mn.sup.4+ which
may have peak wavelength at about 637 nm,
Pb.sub.0.15Ba.sub.1.84Zn.sub.0.01Si.sub.0.99Zr.sub.0.01O.sub.4:Eu
is which may have peak wavelength at around 512 nm, and
Cu.sub.0.2Sr.sub.3.8Al.sub.14O.sub.25:Eu which may have peak
wavelength at about 494 nm.
[0108] In such an embodiment, part of the initial about 405 nm
wavelength emission light from the light emitting diode is absorbed
by the phosphor, and it is converted to longer 2.sup.nd wavelength.
The 1.sup.st and 2.sup.nd light are mixed together and the desire
emission is produced. As the shown FIG. 6, the light emitting
device convert the 1.sup.st UV light of 405 nm wavelength to wide
spectral range of visible light, that is, white light, and at this
time the color temperature is about 3,000K and CRI is about 90 to
about 95.
[0109] FIG. 7 is another embodiment's emission spectrum according
to the invention, which the phosphor is applied for the light
emitting device. The embodiment may have a light emitting diode
with about 455 nm wavelength and the phosphor, which is mixture of
the selected multiple chemical compounds in proper ratio.
[0110] The phosphor is composed of
Cu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu which may have peak
wavelength at about 592 nm,
Pb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu
which may have peak wavelength at about 527 nm, and
Cu.sub.0.05Li.sub.0.002Sr.sub.1.5Ba.sub.0.448SiO.sub.4:Gd, Eu which
may have peak is wavelength at about 557 nm.
[0111] In such an embodiment, part of the initial about 455 nm
wavelength emission light from the light emitting diode is absorbed
by the phosphor, and it is converted to longer 2.sup.nd wavelength.
The 1.sup.st and 2.sup.nd light is mixed together and the desire
emission is produced. As the shown FIG. 7, the light emitting
device convert the 1.sup.st blue light of about 455 nm wavelength
to wide spectral range of visible light, that is, white light, and
at this time the color temperature is about 4,000K to about 6,500K
and CRI is about 86 to about 93.
[0112] The phosphor of the light emitting device according to the
invention can be applied by single chemical compound or mixture of
plurality of single chemical compound besides the embodiments in
relation to FIG. 6 and FIG. 7, which are explained above.
[0113] According to the description above, light emitting device
with wide range of color temperature about 2,000K or about 8,000K
or about 10,000K and superior color rendering index more than about
90 can be realized by using the lead and/or copper doped chemical
compounds containing rare earth elements.
[0114] In such a wavelength conversion light emitting device is
capable of applying on mobile phone, note book and electronic
devices such as home appliance, stereo, telecommunication products,
but also for custom display's key pad and back light application.
Moreover, it can be applied for automobile, medical instrument and
illumination products.
[0115] According to the invention, it is also able to provide a
wavelength conversion light emitting device with stability against
water, humidity, vapor as well as other polar solvents.
[0116] In the foregoing described embodiments, various features are
grouped together in a single embodiment for purposes of
streamlining the disclosure. This method of disclosure is not to be
interpreted as reflecting an intention that the claimed invention
requires more features is than are expressly recited in each claim.
Rather, as the following claims reflect, inventive aspects lie in
less than all features of a single foregoing disclosed embodiment.
Thus, the following claims are hereby incorporated into this
Detailed Description of Embodiments, with each claim standing on
its own as a separate preferred embodiment of the invention.
* * * * *