Patent Grant
9260659
Embodiments of the present invention are directed to red-emitting nitride-based phosphor compositions.
Many of the red-emitting phosphors are derived from silicon nitride (Si3N4). The structure of silicon nitride comprises layers of Si and N bonded in a framework of slightly distorted SiN4 tetrahedra. The SiN4 tetrahedra are joined by a sharing of nitrogen corners such that each nitrogen is common to three tetrahedra. See, for example, S. Hampshire in “Silicon nitride ceramics—review of structure, processing, and properties,” Journal of Achievements in Materials and Manufacturing Engineering, Volume 24, Issue 1, September (2007), pp. 43-50. Compositions of red-emitting phosphors based on silicon nitride often involve substitution of the Si at the center of the SiN4 tetrahedra by elements such as Al; this is done primarily to modify the optical properties of the phosphors, such as the intensity of the emission, and the peak emission wavelength.
There is a consequence of the aluminum substitution, however, which is that since Si4+ is being replaced by Al3+, the substituted compound develops a missing positive charge. There are essentially two ways commonly employed to achieve charge balance: in one scheme, an Al3+ for Si4+ substitution is accompanied by a substitution of O2− for N3−, such that the missing positive charge is counter-balanced with a missing negative charge. This leads to a network of tetrahedra that have either Al3+ or Si4+ as the cations at the centers of the tetrahedra, and a structure whereby either an O2− or an N3− anion is at the corners of the tetrahedra. Since it is not known precisely which tetrahedra have which substitutions, the nomenclature used to describe this situation is (Al,Si)3—(N,O)4. Clearly, for charge balance there is one O for N substitution for each Al for Si substitution.
Furthermore, these substitutional mechanisms for charge balance—O for N—may be employed in conjunction with an interstitial insertion of a cation. In other words, the modifying cation is inserted between atoms preexisting on crystal lattice sites, into “naturally occurring” holes, interstices, or channels. This mechanism does not require an altering of the anionic structure (in other words, a substitution of O for N), but this is not to say that an O for N substitution may not simultaneously occur. Substitutional mechanisms for charge balance may occur in conjunction with an interstitial insertion of a modifier cation.
The use of modifying cations in nitride phosphors of Sr-containing α-SiAlON has been discussed by K. Shioi et al. in “Synthesis, crystal structure, and photoluminescence of Sr-α-SiAlON:Eu2+,” J. Am. Ceram Soc., 93 [2] 465-469 (2010). Shioi et al. give the formula for the overall composition of this class of phosphors: Mm/vSi12-m-nAlm+nOnN16-n:Eu2+, where M is a “modifying cation” such as Li, Mg, Ca, Y, and rare earths (excluding La, Ce, Pr, and Eu), and v is the valence of the M cation. As taught by Shioi et al., the crystal structure of an α-SiAlON is derived from the compound α-Si3N4. To generate an α-SiAlON from α-Si3N4, a partial replacement of Si4+ ions by Al3+ ions takes place, and to compensate for the charge imbalance created by Al3+ substituting for Si4+, some O substitutes N and some positive charges are added by trapping the M cations into the interstices within the network of (Si,Al)—(O,N)4 tetrahedra.
Europium doped alkaline earth metal silicon nitride phosphor with the general formula M2Si5N8:Eu, where M is Ca, Sr, or Ba, have been widely studied, see for example the PhD thesis by J W H van Krevel at the Technical University Eindhoven, January 2000, and H. A. Hoppe, et al., J. Phys. Chem. Solids. 2000, 61:2001-2006. In this family of phosphors, pure Sr2Si5N8:Eu has high quantum efficiency and emits at a peak wavelength of about 620 nm. However, this red nitride phosphor has poor stability when used as a coating on an LED operated at a temperature in the range from 60° C. to 120° C. and an ambient relative humidity in the range from 40% to 90%.
Various research groups have experimented with oxygen-containing M2Si5N8 based phosphor materials, which may also contain other metals. For example, see U.S. Pat. Nos. 7,671,529 and 6,956,247, and U.S. published applications 2010/0288972, 2008/0081011, and 2008/0001126. However, these oxygen containing phosphor materials are known to exhibit poor stability under the combined conditions of high temperature and high relative humidity (RH)—for example 85° C. and 85% RH.
The forms of charge compensation reported in the art are not believed to render the phosphor more impervious to thermal/humidity aging, nor do they appear to accomplish the beneficial result of increasing the peak emission wavelength with little or substantially no alteration of photoemission intensity.
There is a need for silicon nitride-based phosphors and M2Si5N8-based phosphors with peak emission wavelengths over a wider range in the red and also other colors, and with enhanced physical properties of the phosphor, such as temperature and humidity stability.
Embodiments of the present invention may provide {Mg, Ca, Sr, Ba, Y, Li, Na, K, and/or Zn}-stabilized, particularly Ca-stabilized, nitride-based phosphors with chemical composition based on M2Si5N8 with and without column IIIB elements, particularly Al, substituting for Si. The stabilizing cations may be (1) incorporated into the phosphor crystal structure for charge balance for column IIIB element substitution, when used to substitute for Si, and (2) incorporated into the phosphor in excess of any need for charge balancing the substitution of Si by a column IIIB element. These phosphor materials may be configured to extend the peak emission wavelength to longer wavelengths in the red, and to enhance physical properties of the phosphor—notably, significant improvement of the temperature and humidity stability.
Some embodiments of the present invention are directed to a red-emitting phosphor which may comprise a nitride-based composition represented by the chemical formula MxM′2Si5-yAlyN8:A, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, where v is the valence of M, and x>0; M′ is at least one of Mg, Ca, Sr, Ba, and Zn; y satisfies 0≦y≦1.0; and activator A is at least one of Eu, Ce, Tb, Pr, Sm and Mn, wherein x>y/v. Furthermore, the red-emitting phosphor may have the general crystalline structure of M′2Si5N8:A. Yet furthermore, Al may substitute for Si within the general crystalline structure and M may be located within the general crystalline structure substantially at interstitial sites. Furthermore, the red-emitting phosphor may comprise at least one of F, Cl, Br and O. Yet furthermore, M may be Ca, y=0 and 0.1≦x≦0.4. Furthermore, M may be Ca, 0.1≦y≦0.15 and 0.1≦x≦0.4.
Some embodiments of the present invention are directed to a red-emitting phosphor which may comprise a nitride-based composition represented by the chemical formula MaSrbSicAldNeEuf, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0≦c≦5.0; 0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M. Furthermore, the red-emitting phosphor may comprise at least one of F, Cl, Br and O. Yet furthermore, M may be Ca, d=0 and 0.1≦a≦0.4. Furthermore, M may be Ca, 0.1≦d≦0.15 and 0.1≦a≦0.4.
The addition of interstitial Ca to an aluminum substituted M′2Si5N8 red-emitting phosphor, beyond any need for charge balancing for the substitution of Si by Al, has the unexpected benefit that the stability of the phosphor is enhanced under conditions of aging at elevated temperature and humidity. In some embodiments, the phosphor may be compositionally configured such that after 800 hours of aging at 85° C. and 85% relative humidity the drop in photoluminescent intensity is no greater than about 15%, in embodiments no greater than about 10%, and the deviation in chromaticity coordinates CIE Δx and CIE Δy is less than or equal to about 0.015 for each coordinate, in embodiments less than or equal to about 0.010 for each coordinate, and in further embodiments less than or equal to about 0.005 for each coordinate.
Furthermore, the addition of Ca to a M′2Si5N8 red-emitting phosphor has the unexpected benefit that the stability of the phosphor is enhanced under conditions of aging at elevated temperature and humidity. In some embodiments, the phosphor may be compositionally configured such that after 500 hours of aging at 85° C. and 85% humidity the drop in photoluminescent intensity is no greater than about 50%, in embodiments no greater than about 35%, and the deviation in chromaticity coordinates CIE Δx and CIE Δy is less than or equal to about 0.065 for each coordinate, and in embodiments less than or equal to about 0.045 for each coordinate.
According to the present embodiments, the phosphor, under blue excitation, may be configured to emit light having a peak emission wavelength greater than about 620 nm, in embodiments greater than 623 nm, and in further embodiments greater than about 626 nm, where blue may be defined as light having a wavelength ranging from about 420 nm to about 470 nm. The present phosphors may also be excited by radiation having shorter wavelengths; e.g., from about 200 nm to about 420 nm, but when the excitation radiation is in the x-ray or UV, a separate blue-emitting phosphor is provided to contribute a blue component to the desired white light for a white light source. Furthermore, the present phosphors may also be excited by radiation having longer wavelengths, wherein the wavelength ranges from about 200 nm to about 550 nm. A common blue excitation source is an InGaN LED, or GaN LED, emitting with a peak at about 465 nm.
Embodiments of the present invention also include white light emitting device comprising a solid state excitation source and any of the red-emitting phosphors described herein. It may also include a yellow-emitting phosphor and/or a green-emitting phosphor with a peak emission wavelength in the range from about 500 nm to about 580 nm. An exemplary red-emitting phosphor according to embodiments of the present invention is Eu0.05Ca0.1Sr1.95Si4.88Al0.12N8.
These and other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures, wherein:
Embodiments of the present invention will now be described in detail with reference to the drawings, which are provided as illustrative examples of the invention so as to enable those skilled in the art to practice the invention. Notably, the figures and examples below are not meant to limit the scope of the present invention to a single embodiment, but other embodiments are possible by way of interchange of some or all of the described or illustrated elements. Moreover, where certain elements of the present invention can be partially or fully implemented using known components, only those portions of such known components that are necessary for an understanding of the present invention will be described, and detailed descriptions of other portions of such known components will be omitted so as not to obscure the invention. In the present specification, an embodiment showing a singular component should not be considered limiting; rather, the invention is intended to encompass other embodiments including a plurality of the same component, and vice-versa, unless explicitly stated otherwise herein. Moreover, applicants do not intend for any term in the specification or claims to be ascribed an uncommon or special meaning unless explicitly set forth as such. Further, the present invention encompasses present and future known equivalents to the known components referred to herein by way of illustration.
Some embodiments of the present invention are directed to a red-emitting phosphor which may comprise a nitride-based composition represented by the chemical formula MxM′2Si5-yAlyN8:A, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x>0; M′ is at least one of Mg, Ca, Sr, Ba, Y, Li and Zn; 0≦y≦1.0; and A is at least one of Eu, Ce, Tb, Pr, Sm and Mn; wherein x>y/v and v is the valence of M—the latter reflecting the presence of an excess of M for stabilization of the phosphor and a larger amount of M than needed for charge balance of any Al substituting for Si. Furthermore, the red-emitting phosphor may comprise at least one of F, Cl, Br and O. Yet furthermore, the red-emitting phosphor may have the general crystalline structure of M′2Si5N8:A; although embodiments of the red-emitting phosphor may exist with other crystalline structures. Furthermore, Al may substitute for Si within the general crystalline structure and M may be located within the general crystalline structure substantially at interstitial sites.
According to some further embodiments of the present invention, nitride-based calcium-stabilized phosphors may have a composition given by the formula CaxSr2Si5-yAlyN8 where x>0 and 0≦y≦1, wherein the Ca is present in an amount greater than is required to charge balance the substitution of Si by Al, in other words where 2x>y, and wherein the phosphors exhibit good stability under heat and humidity, as specified herein.
According to further embodiments of the present invention, a red-emitting phosphor may comprise a nitride-based composition represented by the chemical formula MaSrbSicAldNeEuf, wherein: M is at least one of Mg, Ca, Sr, Ba, Y Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0c
5.0; 0
d
1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M the latter reflecting the presence of an excess of M for stabilization of the phosphor and a larger amount of M than needed for charge balance of any Al substituting for Si. Furthermore, the red-emitting phosphor may comprise at least one of F, Cl, Br and O. Yet furthermore, M may be Ca, d=0 and 0.1
a≦0.4, and in some embodiments M may be Ca, d=0 and 0.15
a≦0.25. Furthermore, M may be Ca, 0.1
d
0.15 and 0.1
a≦0.4, and in some embodiments M may be Ca, 0.1
d
0.15 and 0.15
a≦0.25.
Some embodiments of the present invention are directed to a nitride-based phosphor composition represented by the general formula MxM′2G5-yDyE8:A, where M is a modifier cation. Advantages of the modification to the 2-5-8 phosphor include an increase in peak emission wavelength towards the deep red end of the spectrum, and an enhanced stability in elevated thermal and humidity conditions.
M is at least one of a 1+ cation, a 2+ cation, and a 3+ cation, and M′ is at least one of Mg, Ca, Sr, Ba, and Zn, used either individually or in combinations. G is at least one of C, Si and Ge, used either individually or in combinations. The element D replaces the G component substitutionally, where D is selected from the group consisting of column IIIB elements of the periodic table of elements. (The labeling of the columns of the periodic table in this disclosure follow the old IUPAC (International Union of Pure and Applied Chemistry) system. See http://en.wikipedia.org/wiki/Group_(periodic_table), last viewed Jan. 15, 2013.) In one embodiment, D is at least one of B, Al, and Ga, used either individually or in combinations. E in the general formula of the present phosphor is at least one of a 3-anion, a 2-anion, and a 1-anion. Specifically, E may be at least one of O2−, N3−, F1−, Cl1−, Br−, and I−, used either individually or in combinations. The activator, A, is at least one of Eu, Ce, Tb, Pr, Sm and Mn. Herein “A” represents a phosphor activator and the notation “:A” represents doping by a rare earth and/or Mn which is generally substitutional, but may also include doping at grain boundaries, on particle surfaces and in interstitial sites within the crystalline structure of the phosphor material. The parameter y is given by 0√y√1.0 and the value of the parameter x may be defined as being greater than the value of y divided by the valence of M, such that M is present in an amount greater than required for charge balance of any substitution of G by D.
The modifier cation M is added to the phosphor in an amount which is greater than is required to charge compensate for the substitution of D for G. Specifically, M may be at least one of Li1+, Na1+, K1+, Sc3+, Ca2+, Sr2+, Ba2+, Zn2+, B3+ and Y3+, used either individually or in combinations. M is an extra cation, utilized in addition to the stoichiometric amount of the divalent metal M′ in the formula M′2Si5N8, and as such, it is expected that this modifier cation might be inserted into the phosphor substantially interstitially, although M may occupy other positions within the host lattice.
Interstitial sites are cavities, holes, or channels that exist in the crystalline lattice by virtue of the manner in which the host's constituent atoms are arranged (packed, or stacked). Dopant atoms that occupy the interstices of a crystal are to be distinguished from such atoms introduced substitutionally; in this latter mechanism, the dopant atoms replace host atoms residing on crystal lattice sites. Support for the proposed interstitial placement of modifier cations within the structure of the phosphor material is found in the literature for ceramic materials with an α-silicon nitride crystal structure. For example, see Hampshire et al. “α′-Sialon ceramics”, Nature 274, 880 (1978) and Huang et al. “Formation of α-Si3N4 Solid Solutions in the System Si3N4—AlN—Y2O3” J. Amer. Ceram. Soc. 66(6), C-96 (1983). These articles state that it is known that the α-silicon nitride unit cell contains two interstitial sites large enough to accommodate other atoms or ions. Furthermore, the α′-sialon structure is derived from the α-silicon nitride structure by partial replacement of Si with Al, and valency compensation is effected by cations—such as Li, Ca, Mg and Y—occupying the interstices of the (Si, Al)—N network, and also by oxygen replacing nitrogen when an oxide is used. (The α′-sialon structure is represented by Mx(Si, Al)12(O, N)16, where x is not greater than 2.) Yet furthermore, it is accepted that the α′-sialon structure requires the equivalent of at least half a cationic valency in each of the two interstices within the unit cell to stabilize the structure.
Generally, the crystalline structures of the 2-5-8 nitride-based compounds as described herein may have a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof. In some examples, the space group is Pmn21. Furthermore, it should be noted that in materials science theory the vacancy density of a pure crystalline material may be on the order of a hundred parts per million of the existing lattice sites depending on the thermal equilibrium conditions of the crystal. As such, a small percentage of the modifier ions, M, may end up in vacant metal ion sites, rather than the interstitial sites—the modifier ions filling the vacancies before the interstitial sites.
Furthermore, the modifier ions may also be involved in charge balancing to compensate for the presence of anions of elements such as F, Cl, Br and O within the phosphor, either substituting for N within the M′2Si5N8 crystal lattice, or filling interstitial positions within the crystal lattice. These anions may either be present in the phosphor material intentionally, or as contaminants. Contaminants, such as oxygen, may be from environmental sources. According to some embodiments, the phosphor may have halide and/or oxygen intentionally introduced in a range from 0 to about 6 mole percent. Halide may be added by using one or more starting materials comprising a halide, for example: EuCl3, EuF3, EuBr3, NH4F, etc. Oxygen may be added by using one or more starting materials comprising an oxide, for example: Eu2O3, SiO2, etc. Furthermore, the methods for controllably incorporating oxygen in to the phosphor material that are described in U.S. patent application Ser. No. 13/871,961 (now U.S. Pat. No. 8,663,502 issued Mar. 4, 2014), incorporated herein by reference in its entirety, may be used for incorporation of oxygen into the phosphors of the present invention.
Next the disclosure will present phosphors based on the present modifier cation-stabilized MxM′2A5-yDyE8:A embodiments, giving their advantages and properties, and how these phosphors differ from the prior art. Specific examples will be given, including a phosphor wherein the column IIIB element substituting for Si4+ is Al3+, and wherein the modifying cation is Ca2+, and other examples in which y=0. Accelerated aging results will be discussed which show the superior thermal and chemical stability of the phosphors of the present invention over other prior art 2-5-8 based phosphors. Finally, SEM micrographs will show the change in morphology of the phosphor crystals as the amount of Ca is increased beyond the amount used to charge balance the substitution of Si by Al.
Discussion of the Present Phosphors Based on CaxSr2Si5-yAlyN8:A
Fifteen different phosphor samples were prepared as described in more detail below with reference to Tables 1A, 1B, 2A, 2B, 3A, 3B, 4A and 4B. PL spectra, CIE coordinates, XRD and SEM data were collected for samples, as discussed in more detail below.
Sample 1 is a well-known 2-5-8 red-emitting nitride phosphor used herein as a control; it has the composition Sr1.95Si5N8Eu0.05. Samples 2 through 5 are based on the composition of Sample 1, but with increasing amounts of calcium added as modifier cations; in these samples the modifier cations do not have a charge compensation role to play, for Si substitution at least. These samples have a composition represented by the formula CaxSr1.95Si5N8Eu0.05.
Samples 6 through 8 are based on the composition of Sample 1, but with calcium substituting for strontium in increasing amounts; in these samples the modifier cations do not have a charge compensation role to play. These samples have a composition represented by the formula CaxSr1.95-xSi5N8Eu0.05. These Samples are compared with Samples 2 through 4 which have the same amount of calcium added, but in Samples 2 through 4 the calcium does not substitute for strontium it is in addition to the strontium and is expected to be present in the phosphor crystal in interstitial lattice positions.
Samples 9 through 12 are based on the composition of Sample 1, but with (1) some aluminum substituted for silicon, and (2) with increasing amounts of calcium added as modifier cations, where the calcium is BOTH playing the role of charge compensation for the substitution of aluminum for silicon, and is present in amounts beyond what is needed for charge compensation and may result in improved phosphor stability under conditions of heat and humidity. These samples have a composition represented by the formula CaxSr1.95Si4.9Al0.1N8Eu0.05.
Samples 13 through 15 are similar to Samples 9 through 12, except for the amount of aluminum being slightly greater in Samples 13 through 15. These samples have a composition represented by the formula CaxSr1.95Si4.88Al0.12N8Eu0.05. Furthermore, Sample 13 has only enough additional calcium to charge compensate the substitution of aluminum for silicon, whereas Samples 14 & 15 have amounts of calcium beyond what is needed for charge compensation.
According to some embodiments, the phosphors, under blue excitation, may be configured to emit light having a peak emission wavelength greater than about 620 nm, in embodiments greater than 623 nm, and in further embodiments greater than about 626 nm, where blue may be defined as light having a wavelength ranging from about 420 nm to about 470 nm. The present phosphors may also be excited by radiation having shorter wavelengths; e.g., from about 200 nm to about 420 nm, but when the excitation radiation is in the x-ray or UV, a separate blue-emitting phosphor is provided to contribute a blue component to the desired white light for a white light source. Furthermore, the present phosphors may also be excited by radiation having longer wavelengths, wherein the wavelength ranges from about 200 nm to about 550 nm. A common blue excitation source is an InGaN LED, or GaN LED, emitting with a peak at about 460 nm.
Reliability Testing
Within many territories including the United States, regulatory bodies set performance criteria for replacement LED lamps. For example the US Environmental Protection Agency (EPA) in conjunction with the US Department of Energy (DOE) promulgates performance specifications under which a lamp may be designated as an “ENERGY STAR®” compliant product, e.g. identifying the power usage requirements, minimum light output requirements, luminous intensity distribution requirements, luminous efficacy requirements, life expectancy, etc. The ENERGY STAR® “Program Requirements for Integral LED Lamps” requires that for all LED lamps “the change of chromaticity over the minimum lumen maintenance test period (6000 hours) shall be within 0.007 on the CIE 1976 (u′,v′) diagram” and depending on lamp type, the lamp must have “≧70% lumen maintenance (L70) at 15,000 or 25,000 hours of operation”. The ENERGY STAR® requirements are for the lamp performance and include all components of the lamp such as the LEDs, phosphor, electronic driver circuitry, optics and mechanical components. In principal, the degradation in brightness of a white LED with aging can be due not only to the phosphor, but also to the blue LED chip. Additional sources of degradation can come from the packaging materials (such as the substrate), the bond wires and other components encapsulated with silicone. In contrast, the factors affecting the change in color coordination are dominated primarily by phosphor degradation. In terms of phosphor performance it is believed that in order to comply with ENERGY STAR® requirements would require a change in chromaticity (CIE Δx, CIE Δy) of 0.01 for each coordinate over 1000 hours for the phosphor under accelerated testing at 85° C. and 85% relative humidity. The accelerated testing is done on phosphor coated 3000K white LEDs prepared as follows: phosphor particles are combined with a binder, such as epoxy or silicone, and then applied to the LED chip. The coated LED is placed in an oven at the specified temperature and humidity and operated continuously for the testing period.
In more detail,
To provide a potential further improvement in performance the particles of the phosphor with the composition of the Samples of the present invention can be coated with one or more coatings of, for example, SiO2, Al2O3 and/or TiO2, as taught in co-pending patent applications U.S. application Ser. No. 13/671,501 (now U.S. Pat. No. 9,006,966 issued Apr. 14, 2015) for COATINGS FOR PHOTOLUMINESCENT MATERIALS and U.S. application Ser. No. 13/273,166 (published as U.S. Pub. No. 2013/0092964 A1 on Apr. 18, 2013) for HIGHLY RELIABLE PHOTOLUMINESCENT MATERIALS HAVING A THICK AND UNIFORM TITANIUM DIOXIDE COATING, the content of each of which is incorporated in its entirety by way of reference thereto.
XRD of the Present Phosphor Compositions
Morphology of Phosphor Particles of the Present Phosphor Compositions
Synthesis of the Present Phosphors
For each of the examples and comparative examples described herein, the starting materials included at least one of the compounds Si3N4, AlN, Ca3N2, Sr3N2, BN, GaN, SiO2, Al2O3, and EuCl3.
Samples 1 Through 5
To obtain desired compositions of the phosphors exemplified in Samples 1 through 5, solid powders were weighed according to the compositions listed in Table 1A. This mixture of raw materials were then loaded into a plastic milling bottle together with milling beads, sealed in a glove box, followed by a ball milling process for about 2 hours. The mixed powders were then loaded into a molybdenum crucible having an inner diameter of 30 mm and a height of 30 mm; the loaded crucible was covered with a molybdenum lid and placed into a gas sintering furnace equipped with a graphite heater.
After loading the crucible, the furnace was evacuated to 10−2 Pa, and the sample heated to 150° C. under these vacuum conditions. At the 150° C. temperature, a high purity N2 gas was introduced into the chamber; the temperature of the furnace was then increased to about 1700° C. at a substantially constant heating rate of 4° C./min. The samples were maintained at 1700° C. for about 7 hours.
After firing, the power was shut off and the samples allowed to cool in the furnace. The as-sintered phosphor was ground slightly, ball milled to a certain particle size, followed by a wash, dry and sieve procedure. The final product was tested using an Ocean Optics USB4000 spectrometer for photoluminescence intensity (PL) and chromaticity (CIE coordinates x and y). The x-ray diffraction (XRD) patterns of the phosphors were measured using the Kα line of a Cu target. The test results are listed in Table 1B.
A flux, such as ammonium chloride, may also be used in the fabrication of the phosphors of the present invention.
Samples 6 Through 8
To obtain the desired compositions of the phosphors of Samples 6 through 8, solid powders were weighed according to the compositions listed in Table 2A. The same synthesis procedure as that used for Samples 1 through 5 was used. The test results are listed in Table 2B.
The emission spectra of phosphor Samples 6 through 8 are shown in
Samples 9 Through 12
To obtain the desired compositions of the phosphors of Samples 9 through 12, solid powders were weighed according to the compositions listed in Table 3A. The same synthesis procedure as that used for Samples 1 through 5 was used. The test results are listed in Table 3B.
Samples 13 Through 15
To obtain the desired compositions of the phosphors of Samples 13 through 15, solid powders were weighed according to the compositions listed in Table 4A. The same synthesis procedure as that used for Samples 1 through 5 was used. The test results are listed in Table 4B.
Those of ordinary skill in the art will appreciate that compositions beyond those specifically described above may be made using the methods described above with some different choices of elements. For example, phosphor compositions may be made which are represented by the chemical formula MaSrbSicAldNeEuf, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0≦c≦5.0; 0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M. Furthermore, phosphor compositions may be made which are represented by the chemical formula MxM′2Si5-yAlyN8:A, wherein: M is Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x>0; M′ is at least one of Mg, Ca, Sr, Ba, and Zn; 0≦y≦0.15; and A is at least one of Eu, Ce, Tb, Pr, and Mn; wherein x>y/v and v is the valence of M, and wherein the phosphors have the general crystalline structure of M′2Si5N8:A.
The device 100 further comprises a plurality (four in the example illustrated) of blue light emitting LEDs 112 (blue LEDs) that are mounted in thermal communication with a circular-shaped MCPCB (metal core printed circuit board) 114. The blue LEDs 112 can comprise a ceramic packaged array of twelve 0.4W GaN-based (gallium nitride-based) blue LED chips that are configured as a rectangular array 3 rows by 4 columns.
To maximize the emission of light, the device 100 can further comprise light reflective surfaces 116 and 118 that respectively cover the face of the MCPCB 114 and the inner curved surface of the top 108. The device 100 further comprises a photoluminescent wavelength conversion component 120 that is operable to absorb a proportion of the blue light generated by the LEDs 112 and convert it to light of a different wavelength by a process of photoluminescence. The emission product of the device 100 comprises the combined light generated by the LEDs 112 and the photoluminescent wavelength conversion component 120. The wavelength conversion component is positioned remotely to the LEDs 112 and is spatially separated from the LEDs. In this patent specification “remotely” and “remote” means in a spaced or separated relationship. The wavelength conversion component 120 is configured to completely cover the housing opening such that all light emitted by the lamp passes through the component 120. As shown the wavelength conversion component 120 can be detachably mounted to the top of the wall portion 106 using the top 108 enabling the component and emission color of the lamp to be readily changed.
According to embodiments of the invention, a red-emitting phosphor may comprise a nitride-based composition represented by the chemical formula MaSrbSicAldNeEuf, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0≦c≦5.0; 0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M. The red-emitting phosphor may further comprise at least one of F, Cl, Br and O. Furthermore, the red-emitting phosphor may be the phosphor wherein M is Ca, d=0 and 0.1≦a≦0.4; in embodiments the red-emitting phosphor may be selected from the group consisting of: Eu0.05Ca0.1Sr1.95Si5N8; Eu0.05Ca0.2Sr1.95Si5N8; Eu0.05Ca0.3Sr1.95Si5N8; and Eu0.05Ca0.4Sr1.95Si5N8; in further embodiments the red-emitting phosphor may absorb radiation at a wavelength ranging from about 200 nm to about 550 nm and emit light with a photoluminescence peak emission wavelength greater than 620.0 nm. Furthermore, the red-emitting phosphor may be the phosphor wherein M is Ca, 0.1≦d≦0.15 and 0.1≦a≦0.4; in embodiments the red-emitting phosphor may be selected from the group consisting of: Eu0.05Ca0.1Sr1.95Si4.9Al0.1N8; Eu0.05Ca0.2Sr1.95Si4.9Al0.1N8; Eu0.05Ca0.3Sr1.95Si4.9Al0.1N8; Eu0.05Ca0.4Sr1.95Si4.9Al0.1N8; Eu0.05Ca0.1Sr1.95Si4.88Al0.12N8; and Eu0.05Ca0.2Sr1.95Si4.88Al0.12N8; in further embodiments the red-emitting phosphor may be configured such that under excitation by a blue LED the reduction in photoluminescent intensity after 800 hours of aging at about 85° C. and about 85% humidity is no greater than about 15%; in yet further embodiments the red-emitting phosphor may be configured such that the deviation in chromaticity coordinates CIE Δx and CIE Δy after 800 hours of aging at about 85° C. and about 85% relative humidity is less than or equal to about 0.015 for each coordinate, and in embodiments wherein the deviation in chromaticity coordinates CIE Δx and CIE Δy is less than or equal to about 0.005 for each coordinate; in further embodiments the red-emitting phosphor may absorb radiation at a wavelength ranging from about 200 nm to about 550 nm and emit light with a photoluminescence peak emission wavelength greater than 620.0 nm. Furthermore, the red-emitting phosphor may be the phosphor wherein the red-emitting phosphor has the general crystalline structure of Sr2Si5N8:Eu with M and Al incorporated therein; in embodiments Al may substitute for Si within the general crystalline structure and M may be located within the general crystalline structure substantially at interstitial sites. Furthermore, the red-emitting phosphor may consist of Ca, Sr, Si, Al, N, Eu and at least one of F, Cl, Br and O.
According to further embodiments of the invention, a red-emitting phosphor may comprise a nitride-based composition represented by the chemical formula MxM′2Si5-yAlyN8:A, wherein: M is at least one of Mg, Ca, Sr, Ba, Y and Li, and x>0; M′ is at least one of Mg, Ca, Sr, Ba, Y and Li; 0y
1; and A is at least one of Eu, Ce, Tb, Pr, Sm and Mn; wherein x>y/v and v is the valence of M, and wherein the red-emitting phosphor has the general crystalline structure of M′2Si5N8:A. Furthermore, the red-emitting phosphor may be the phosphor wherein M is the same as M′. Furthermore, the red-emitting phosphor may absorb radiation at a wavelength ranging from about 200 nm to about 550 nm and emit light with a photoluminescence peak emission wavelength greater than 620.0 nm. Furthermore, the red-emitting phosphor may be configured such that the deviation in chromaticity coordinates CIE Δx and CIE Δy after 800 hours of aging at about 85° C. and about 85% relative humidity is less than or equal to about 0.015 for each coordinate, and in embodiments the deviation in chromaticity coordinates CIE Δx and CIE Δy may be less than or equal to about 0.005 for each coordinate. Furthermore, the red-emitting phosphor may further comprise at least one of F, Cl, Br and O. Furthermore, the red-emitting phosphor may consist of Ca, Sr, Si, Al, N, Eu and at least one of F, Cl, Br and O. Furthermore, the red-emitting phosphor may be the phosphor wherein M′ is Sr, and in embodiments wherein M is Ca. Furthermore, the red-emitting phosphor may be the phosphor wherein RE is Eu. Furthermore, the red-emitting phosphor may be the phosphor wherein y=0 and 0.1
x
0.4. Furthermore, the red-emitting phosphor may be the phosphor wherein 0.1
y
0.15 and 0.1
x
0.4.
According to yet further embodiments, a white light emitting device may comprise: a solid state excitation source with emission wavelength within a range from 200 nm to 480 nm; a red-emitting phosphor comprising a nitride-based composition represented by the chemical formula MaSrbSicAldNeEuf, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0≦c≦5.0; 0≦d≦1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M; the red-emitting phosphor being configured to absorb excitation radiation from the excitation source and to emit light having a peak emission wavelength in the range from about 620 nm to about 650 nm; and a yellow/green-emitting phosphor having a peak emission wavelength in the range from about 500 nm to about 580 nm. Furthermore, the white light emitting device may have the red-emitting phosphor configured to absorb excitation radiation from the excitation source and to emit light having a peak emission wavelength in the range from about 624 nm to about 632 nm. Furthermore, the white light emitting device may have the red-emitting phosphor with the formula Eu0.05Ca0.1Sr1.95Si4.88Al0.12N8. Furthermore, the white light emitting device may have the excitation source with an emission wavelength within a range from 450 nm to 470 nm.
Although the present invention has been particularly described with reference to certain embodiments thereof, it should be readily apparent to those of ordinary skill in the art that changes and modifications in the form and details may be made without departing from the spirit and scope of the invention.
This application is a continuation of U.S. patent application Ser. No. 13/922,231 filed Jun. 19, 2013 (now U.S. Pat. No. 8,597,545), which is a continuation-in-part of U.S. patent application Ser. No. 13/871,961 filed Apr. 26, 2013 (now U.S. Pat. No. 8,663,502), which claims the benefit of U.S. Provisional Application No. 61/673,191 filed Jul. 18, 2012. The disclosures of the aforementioned applications are all incorporated by reference in their entirety herein.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3207583 | Brautigam | Sep 1965 | A |
| 6649946 | Bogner et al. | Nov 2003 | B2 |
| 6670748 | Ellens et al. | Dec 2003 | B2 |
| 6956247 | Stockman | Oct 2005 | B1 |
| 7026755 | Setlur et al. | Apr 2006 | B2 |
| 7138756 | Gotoh et al. | Nov 2006 | B2 |
| 7229573 | Setlur et al. | Jun 2007 | B2 |
| 7252787 | Hancu et al. | Aug 2007 | B2 |
| 7252788 | Nagatomi et al. | Aug 2007 | B2 |
| 7258816 | Tamaki | Aug 2007 | B2 |
| 7311858 | Wang et al. | Dec 2007 | B2 |
| 7345418 | Nagatomi et al. | Mar 2008 | B2 |
| 7476337 | Sakane et al. | Jan 2009 | B2 |
| 7476338 | Sakane et al. | Jan 2009 | B2 |
| 7507354 | Oshio | Mar 2009 | B2 |
| 7537710 | Oshio | May 2009 | B2 |
| 7540977 | Hirosaki et al. | Jun 2009 | B2 |
| 7556744 | Tamaki et al. | Jul 2009 | B2 |
| 7575679 | Sumino et al. | Aug 2009 | B2 |
| 7597823 | Tamaki et al. | Oct 2009 | B2 |
| 7671529 | Mueller et al. | Mar 2010 | B2 |
| 7700002 | Schmidt et al. | Apr 2010 | B2 |
| 7713443 | Hirosaki et al. | May 2010 | B2 |
| 7854859 | Kameshima et al. | Dec 2010 | B2 |
| 8062549 | Nagatomi et al. | Nov 2011 | B2 |
| 8076847 | Tamaki et al. | Dec 2011 | B2 |
| 8153025 | Schmidt et al. | Apr 2012 | B2 |
| 8178001 | Kaneda et al. | May 2012 | B2 |
| 8475683 | Li et al. | Jul 2013 | B2 |
| 8597545 | Liu et al. | Dec 2013 | B1 |
| 20050189863 | Nagatomi et al. | Sep 2005 | A1 |
| 20060017365 | Nagatomi et al. | Jan 2006 | A1 |
| 20060027786 | Dong et al. | Feb 2006 | A1 |
| 20060145123 | Cheng et al. | Jul 2006 | A1 |
| 20060255710 | Mueller-Mach et al. | Nov 2006 | A1 |
| 20070007494 | Hiosaki et al. | Jan 2007 | A1 |
| 20070029526 | Cheng et al. | Feb 2007 | A1 |
| 20070040152 | Oshio | Feb 2007 | A1 |
| 20070182309 | Wang et al. | Aug 2007 | A1 |
| 20070257596 | Shimomura et al. | Nov 2007 | A1 |
| 20080001126 | Hirosaki | Jan 2008 | A1 |
| 20080081011 | Oshio | Apr 2008 | A1 |
| 20080116786 | Wang et al. | May 2008 | A1 |
| 20080128726 | Sakata et al. | Jun 2008 | A1 |
| 20080143246 | Hirosaki et al. | Jun 2008 | A1 |
| 20080303409 | Hirosaki et al. | Dec 2008 | A1 |
| 20090114929 | Lee et al. | May 2009 | A1 |
| 20090166584 | Shimooka et al. | Jul 2009 | A1 |
| 20090243467 | Shimizu et al. | Oct 2009 | A1 |
| 20090251044 | Shioi | Oct 2009 | A1 |
| 20090267485 | Nagatomi et al. | Oct 2009 | A1 |
| 20090283721 | Liu et al. | Nov 2009 | A1 |
| 20090309112 | Yoshimatsu | Dec 2009 | A1 |
| 20090322209 | Becker et al. | Dec 2009 | A1 |
| 20090322990 | Kawana et al. | Dec 2009 | A1 |
| 20100039020 | Hirosaki | Feb 2010 | A1 |
| 20100044729 | Naum et al. | Feb 2010 | A1 |
| 20100052515 | Watanabe et al. | Mar 2010 | A1 |
| 20100085728 | Seto et al. | Apr 2010 | A1 |
| 20100123104 | Collins et al. | May 2010 | A1 |
| 20100187974 | Zhang et al. | Jul 2010 | A1 |
| 20100213822 | Shimooka et al. | Aug 2010 | A1 |
| 20100288972 | Roesler et al. | Nov 2010 | A1 |
| 20100296024 | Ishimaru et al. | Nov 2010 | A1 |
| 20110001154 | Kim et al. | Jan 2011 | A1 |
| 20110031874 | Hosokawa et al. | Feb 2011 | A1 |
| 20110176084 | Akiho et al. | Jul 2011 | A1 |
| 20120104929 | Yeh et al. | May 2012 | A1 |
| 20120112130 | Wu et al. | May 2012 | A1 |
| 20120262904 | Van Woudenberg et al. | Oct 2012 | A1 |
| 20130092964 | Li et al. | Apr 2013 | A1 |
| 20130127332 | Chen et al. | May 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 101157854 | Apr 2008 | CN |
| 102433114 | May 2012 | CN |
| 1568753 | Aug 2005 | EP |
| 1837386 | Sep 2007 | EP |
| 1873225 | Jan 2008 | EP |
| 1884552 | Feb 2008 | EP |
| 1887067 | Feb 2008 | EP |
| 2009077 | Dec 2008 | EP |
| 2058382 | May 2009 | EP |
| 2471890 | Jul 2012 | EP |
| 2003124527 | Apr 2003 | JP |
| 2004-244560 | Sep 2004 | JP |
| 2005-226000 | Aug 2005 | JP |
| 200641096 | Feb 2006 | JP |
| 2007169428 | Jul 2007 | JP |
| 2008-163259 | Jul 2008 | JP |
| 4543251 | Jul 2010 | JP |
| 2012-046626 | Mar 2012 | JP |
| 2012-069572 | Apr 2012 | JP |
| 2012-114333 | Jun 2014 | JP |
| 10-2010-0086964 | Aug 2010 | KR |
| Entry |
|---|
| Hampshire, “α—Sialon Ceramics”, Nature, vol. 274, Aug. 31, 1978, pp. 880-882. |
| Hecht, Cora “SrALS14N7:EU2+—a Nitridoaluminosilicate Phosphor for Warm White Light . . . ”, Chem. Mater, 21, 2009, pp. 1595-1601. |
| Huang, et a., “Formation of α—Si3N4 Solid Solutions in the System Si3N4—A1N—Y2O3”, Comm. of the American Cerm. Soc., Jun. 1983, C96-C97. |
| Piao, et al., “Preparation of (Sr1-xCax)2Si5N8:Eu2+ Solid Solutions and Their Luminescence Properties,”, J. of the Electrochem. Soc., 152(12), 2006, pp. H232-H235. |
| Ruan, J., et al., “Nitrogen Gas Pressure Synthesis and Photoluminescent Properties of Orange-Red SrALSi4N7:Eu2+ Phosphors for White Light Emitting Diodes”, J. Am. Ceram. Soc, 94(2), 2011, pp. 536-542. |
| Shioi, K., et al., “Synthesis Crystal Structure and Photoluminescence of Sr—α—SiA1ON:Eu2+”, J. Am. Ceramic Soc., 93(2), 2010, pp. 465-469. |
| Xie, et al., “A Simple, Efficient Synthetic Route to Sr2Si5N8:Eu2+—based Red Phosphors for White Light-Emitting Diodes”, Chem. Mater., 18, 2006, pp. 5578-5583. |
| Hampshire, et al., “Silicon Nitride Cereamics-Review of Structure, Processing and Properties”, J. of Achievements in Mats. and Manufacturing Engineering, 24(1), Sep. 2007, pp. 43-50. |
| Hoppe, et al., “Luminescence in Eu2+—doped Ba2Si5N8 Fluoresence, Thermoluminescence and Upconversion”, J. of Phys. Chem. Solids, vol. 61, 2000, pp. 2001-2006. |
| Li et al., “Luminesecnece Properties of Red-Emitting M2Si5N8EU2+(M=Ca, Sr, Ba), LED Conversion Phosphors”, J. of Alloys and Compounds, 2006, pp. 273-279, vol. 417. |
| Piao, et al., “Synthesis and Luminescent Properties of Low Oxygent Contained Eu2+-doped Ca—α—SiAlON Phosphor from Calcium Cynanamide Reduction”, J. of Rare Earths, 26(2), Apr. 2008, pp. 198-202. |
| Uheda, et al., “Luminescence Properties of a Red Phosphor CaAlSiN3 Eu2+, for White Light-Emitting diodes”, Electrochem. and Solid State Letts., 2006, pp. H22-H25, 9(4). |
| Van Krevel, “On New Rare Earth Doped M—Si—Ai—O—N Materials: Luminescence Properties and Oxidation Resistance”, Thesis, Chapters 1-3, 200, pp. 1-43, 2000. |
| Xie, Rong-Jun, et al., “Silicon-based Oxynitride and Nitride Phosphors for White LEDs—a Review”, Science and Tech. of Advanced Mats., Oct. 23, 2007, vol. 8, pp. 588-600. |
| International Search Report and Written Opinion issued Oct. 22, 2013 in corresponding PCT/US2013/050789. |
| Number | Date | Country | |
|---|---|---|---|
| 20140084783 A1 | Mar 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61673191 | Jul 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13922231 | Jun 2013 | US |
| Child | 14095766 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13871961 | Apr 2013 | US |
| Child | 13922231 | US |
