# Patent

## Title
Nitride phosphors with interstitial cations for charge balance

## Abstract

Phosphors comprising a nitride-based composition represented by the chemical formula: M(x/v)(M′aM′′b)Si(c−x)AlxNd:RE, wherein: M is a divalent or trivalent metal with valence v; M′ is at least one divalent metal; M′′ is at least one trivalent metal; 2a+3b+4c=3d; and RE is at least one element selected from the group consisting of Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb. Furthermore, the nitride-based composition may have the general crystalline structure of M′aM′′bSicNd, where Al substitutes for Si within the crystalline structure and M is located within the crystalline structure substantially at the interstitial sites.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 13/732,222 filed Dec. 31, 2012, now U.S. Pat. No. 8,951,441, which claims the benefit of U.S. Provisional Application No. 61/582,198 filed Dec. 30, 2011, both of which are incorporated herein by reference in their entirety.


FIELD OF THE INVENTION
Embodiments of the present invention relate generally to nitride phosphors and methods for preparing such phosphors.
BACKGROUND OF THE INVENTION
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 has a missing positive charge. Since nature does not allow unbalanced electrical charges in materials, this missing positive charge has to be balanced in some manner. An approach used to achieve charge balance requires the Al3+ for Si4+ substitution to be 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 cation is inserted between atoms preexisting on crystal lattice sites, into “naturally occurring” holes, interstices, or channels. For example, the use of cations in Sr-containing α-SiAlONs have 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 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 (what Shioi et al. refer to as “stabilization”) by trapping the M cations into the interstices within the network of (Si,Al)—(O,N)4 tetrahedra.
The discovery of the europium doped alkaline earth metal silicon nitride phosphor (M2Si5N8 where M is Ca, Sr, or Ba) was made in 2000 by several groups, one of which produced the PhD thesis by J. W. H. van Krevel at the Technical University Eindhoven, January 2000, Osram Opto Semiconductors U.S. Pat. No. 6,649,946, and H. A. Hoppe, et al., J. Phys. Chem. Solids. 2000, 61:2001-2006. This family of phosphors emits at wavelengths from 600 nm to 650 nm with high quantum efficiency. Among them, pure Sr2Si5N8 had the highest quantum efficiency and emitted at a peak wavelength of about 620 nm. It is well known that this red nitride phosphor has poor stability under the conditions wherein the LED is operated at a temperature ranging from 60 to 120′C and an ambient humidity ranging from 40 to 90%.
U.S. Pat. No. 8,076,847 (the '847 patent) to Tamaki et al. is directed to a nitride phosphor represented by the general formula LxMyN((2/3)X+(4/3)Y):R or LXMYOZN((2/3)X+(4/3)Y−(2/3)Z):R, wherein L is at least one or more selected from the Group II elements consisting of Mg, Ca, Sr, Ba and Zn, M is at least one or more selected from the Group IV Elements in which Si is essential among C, Si and Ge, and R is at least one or more selected from the rare earth elements in which Eu is essential among Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Lu. Various embodiments of the patent further contain a Group I[A] element consisting of Li, Na, K, Rb, and Cs. This Group I[A] element functions as a flux during synthesis and not as an interstitial cation for charge balance, the purpose of the flux being to control the particle diameter.
US 2010/0288972 to Roesler et al. teach a AE2Si5N8:RE phosphor with a charge compensation mechanism that counters a charge imbalance caused by oxygen, whether introduced intentionally or non-intentionally. If the oxygen is introduced non-intentionally then it is a contamination, but in either event, the charge imbalance caused by the replacement of nitrogen (N3−) with oxygen (O2−) has to be balanced. Roesler et al. accomplish this in US 2010/0288972 either by the substitutional replacement of silicon (Si4+) with a column IIIB element, such as aluminum (A3+), or by the replacement of the alkaline earth content originally present in the phosphor (e.g., Sr2+ or Ca2+) by an alkali metal (such as Li+, Na+, or K+). Note that the authors reported no shift in the peak emission wavelength as a result of the substitutions and charge balancing, and further, no enhanced stability was reported with accelerated environmental stress testing (e.g., temperature and humidity aging).
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 stabilized silicon nitride-based phosphors and stabilized 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.
SUMMARY OF THE INVENTION
Embodiments of the invention generally provide nitride-based phosphors and methods for forming such nitride-based phosphors. The nitride-based phosphors emit fluorescent light in at least the red, orange, yellow and green regions of the electromagnetic spectrum. The nitride-based phosphors may be used in light emitting diode (LED) devices.
In general, the present invention is based on the substitution of Si by Al in Sr2Si5N8:RE, Si3N4:RE, and related phosphor compounds, with Li, Na, K, Mg, Ca, Sr, Y, or other small metal ions and the combinations of these metal ions being incorporated into the crystal lattice substantially at the interstitial sites to provide charge balance—compensating for the charge imbalance due to substitution of Si by Al. The interstitial metal may also contribute to improved thermal and chemical stability of the crystal structure.
Embodiments of the present invention may be described generally as phosphors comprising a nitride-based composition represented by the chemical formula: M(x/v)(M′aM′′b)Si(c−x)AlxNd:RE, wherein: M is a monovalent, divalent or trivalent metal with valence v; M′ is at least one divalent metal; M′′ is at least one trivalent metal; 2a+3b+4c=3d; and RE is at least one element selected from the group consisting of Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb. Furthermore, the nitride-based composition may have the general crystalline structure of M′aM′′bSicNd, where Al substitutes for Si within the crystalline structure and M is located within the crystalline structure substantially at the interstitial sites. Yet furthermore, M may be selected from the group consisting of Li, Na, K, Ca, Sr, Mg, Ba, Zn, Sc, Y, Lu, La, Ce, Gd, Sm, Pr, Th, and Yb, M′ may be selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and M′′ may be selected from the group consisting of Sc, Y, Lu, La, Gd, Th, Sm, Pr, Yb and Bi. Furthermore, x may satisfy 0.01≦x≦0.6c. Some examples of compositions according to embodiments of the present invention are: Mx/2M′Si1−xAlxN2:RE; Mx/2M′M′′Si1−xAlxN3:RE; Mx/2M′′Si3−xAlxN5:RE; Mx/2M′2M′′Si2−xAlxN5:RE; Mx/2M′Si4−xAlxN6:RE; Mx/2M′′4Si3−xAlxN8:RE; Mx/2M′6Si3−xAlxN8:RE; Mx/2M′3M′′2Si3−xAlxN8:RE; Mx/2M′′3Si3−xAlxN7:RE; Mx/2M′3M′′Si3−xAlxN7:RE; Mx/2M′2M′′Si5−xAlxN9:RE; Mx/2M′M′′3Si4−xAlxN9:RE; Mx/2M′′Si6−xAlxN9:RE; Mx/2M′′3Si6−xAlxN11:RE; and Mx/2M′M′′Si5−xAlxN11:RE.
In one embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8, (note that this formula may be rewritten in the format of the general formula, M(x/v)(M′aM′′b)Si(c−x)AlxNd:RE, as Ca0.5x(Cax′′Sr1−x′′)2−x′Eux′Si5−xAlxN8, similarly all formulas provided herein may be rewritten in this format) wherein 0.1≦x≦1.3, 0.00001≦x′≦0.2, and 0≦x′′≦1, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8 is more narrowly represented wherein 0.3≦x≦1.3, 0.0001≦x′≦0.1, and 0.05≦x′′≦0.4, more narrowly wherein 0.5≦x≦1.3, 0.001≦x′≦0.1, and 0.1≦x′′≦0.3, and more narrowly wherein 0.7≦x≦1.3, for example, wherein 1.0≦x≦1.3 or wherein 1.05≦x≦1.25.
The nitride-based compounds of the phosphor may have a crystalline structure with a single phase or a mixed phase and include a 2-5-8 phase in pure or mixed form. The nitride-based compounds described herein distinguish previous nitride phosphors having a 1-1-1-3 phase or CASN phase (e.g., CaSiAlN3)—which generally have the space group Cmc21. Generally, the crystalline structures of the 2-5-8 nitride-based compounds as described herein have a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof. In some examples, the space group is Pmn21.
In another embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula REx′(Cax′′Sr(1−x′′))(2+0.5x−x′′)Si(5−x)AlxN8, wherein RE is at least one element selected from Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof, 0.1≦x≦3, 0.00001≦x′≦0.2, and 0≦x′′≦1, and the nitride-based compound has a crystalline structure having a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites. A phosphor activator is represented by RE which contains one element, two elements, or more elements for activating the nitride-based compound of the phosphor. In some examples, the phosphor activator contains Eu and at least one or more elements. Therefore, the RE is Eu and one or more elements selected from Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof. In some examples, the chemical formula REx′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8 is more narrowly represented wherein 0.3≦x≦2.5, 0.0001≦x′≦0.1, and 0≦x′′≦1, more narrowly wherein 1≦x≦2, 0.001≦x′≦0.1, and 0.05≦x′′≦0.4, more narrowly wherein x=2, 0.001≦x′≦0.1, and 0.1≦x′′≦0.3.
In another embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′′)Si(5−x)AlxN8, wherein 0.1≦x≦3, 0.00001≦x′≦0.2, and 0≦x′′≦1, and the nitride-based compound has a crystalline structure having a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites. In another embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula Eux′(Cax′′Sr(1−x′′))(3−x′)Si3Al2N8, wherein 0.00001≦x′≦0.2, and 0≦x′′≦1, and the nitride-based compound has a crystalline structure having a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites.
In another embodiment, a phosphor (e.g., an orange phosphor) containing a nitride-based compound is represented by the chemical formula REx′Ca(0.5x−x′)Si(3−x)AlxN4, wherein RE is at least one element selected from Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof, 0.1<x<3, and 0.0001≦x′≦0.2, and wherein the nitride-based compound has the general crystalline structure of α-Si3N4 (i.e. an α-Si3N4 structure), Al substitutes for Si within said crystalline structure, and the Ca atoms are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula REx′Ca(0.5x−x′)Si(3−x)AlxN4 is more narrowly represented wherein 0.1<x<3 and 0.0001≦x′≦0.2, more narrowly wherein 0.2≦x≦2 and 0.001≦x′≦0.1, more narrowly wherein 0.3≦x≦1.8 and 0.005≦x′≦0.1, and more narrowly wherein 0.3≦x≦1.8 and x′=0.03.
In another embodiment, a phosphor (e.g., a green phosphor) containing a nitride-based compound is represented by the chemical formula REx′Sr(0.5x−x′)Si(3−x)AlxN4, wherein RE is at least one element selected from Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof, 0.1<x<3, and 0.0001≦x′≦0.2, and wherein said nitride-based compound has the general crystalline structure of α-Si3N4, Al substitutes for Si within said crystalline structure, and the Sr atoms are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula REx′Sr(0.5x−x′)Si(3−x)AlxN4 is more narrowly represented wherein 0.1<x<3 and 0.0001≦x′≦0.2, more narrowly wherein 0.2≦x≦2 and 0.001≦x′≦0.1, more narrowly wherein 0.3≦x≦1.8 and 0.005≦x′≦0.1, and more narrowly wherein 0.3≦x≦1.8 and x′=0.03.
Methods for preparing the nitride-based phosphors of the present invention are disclosed herein.



BRIEF DESCRIPTION OF THE DRAWINGS
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:
FIG. 1 depicts an emission spectra of Eu:Ca(2+0.5x)Si(5−x)AlxN8 with different x values, as described by embodiments herein;
FIGS. 2A-2B depict emission spectra of Eu0.05(SrxCa(1−x))2.95Si3Al2N8, with different x values, as described by embodiments herein;
FIGS. 3A-3B depict emission spectra of Eux(Sr0.8Ca0.2)3−xSi3Al2N8, with different x values, as described by embodiments herein;
FIG. 3C depicts an XRD pattern of Eux(Sr0.8Ca0.2)3−xSi3Al2N8, with different x values, as described by embodiments herein;
FIG. 4 depicts emission spectra of Ca((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03, with different x values, as described by embodiments herein; and
FIG. 5 depicts emission spectra of Sr((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03, with different x values, as described by embodiments herein.



DETAILED DESCRIPTION OF THE INVENTION
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.
Embodiments of the invention generally provide nitride-based phosphors and methods for forming such nitride-based phosphors. The nitride-based phosphors emit fluorescent light in at least the red, orange, and green regions of the electromagnetic spectrum. The nitride-based phosphors may be used in light emitting diode (LED) devices.
In general, the present invention is based on the substitution of Si by Al in Sr2Si5N8:RE, Si3N4:RE, and related phosphor compounds, with Li, Na, K, Mg, Ca, Sr, Y, or other small metal ions and the combinations of these metal ions being incorporated substantially at the interstitial sites into the crystal lattice to provide charge balance—compensating for the charge imbalance due to substitution of Si by Al. The interstitial metal may also contribute to improved thermal and chemical stability of the crystal structure. The substitution and charge balance is effected while maintaining the same general crystal structure of the unsubstituted material. (Note 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 charge balance ions may actually end up in vacant metal ion sites, rather than the interstitial sites—the charge balance ions filling the vacancies before the interstitial sites.)
Support for this proposed 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.
Embodiments of the present invention may be described generally as phosphors comprising a nitride-based composition represented by the chemical formula: M(x/v)(M′aM′′b)Si(c−x)AlxNd:RE, wherein: M is a monovalent, divalent or trivalent metal with valence v; M′ is at least one divalent metal; M′′ is at least one trivalent metal; 2a+3b+4c=3d; and RE is at least one element selected from the group consisting of Eu, Ce, Pr, Nd, Sm, Gd, Th, Dy, Ho, Er, Tm, Yb. Furthermore, the nitride-based composition may have the general crystalline structure of M′aM′′bSicNd, where Al substitutes for Si within the crystalline structure and M is located within the crystalline structure substantially at the interstitial sites. Yet furthermore, M may be selected from the group consisting of Li, Na, K, Ca, Sr, Mg, Ba, Zn, Sc, Y, Lu, La, Ce, Gd, Sm, Pr, Tb, and Yb, M′ may be selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and M′′ may be selected from the group consisting of Sc, Y, Lu, La, Gd, Tb, Sm, Pr, Yb and Bi. Furthermore, x may satisfy 0.01≦x≦0.6c. Some examples of compositions according to embodiments of the present invention are: Mx/2M′Si1−xAlxN2:RE; Mx/2M′M′′Si1−xAlxN3:RE; Mx/2M′′Si3−xAlxN5:RE; Mx/2M′2M′′Si2−xAlxN5:RE; Mx/2M′Si4−xAlxN6:RE; Mx/2M′′4Si3-xAlxN8:RE; Mx/2M′6Si3−xAlxN8:RE; Mx/2M′3M′′2Si3−xAlxN8:RE; Mx/2M′′3Si3−xAlxN7:RE; Mx/2M′3M′′Si3−xAlxN7:RE; Mx/2M′2M′′Si5−xAlxN9:RE; Mx/2M′M′′3Si4−xAlxN9:RE; Mx/2M′′Si6−xAlxN9:RE; Mx/2M′′3Si6−xAlxN11:RE; and Mx/2M′M′′Si5−xAlxN11:RE.
Some specific embodiments of the present invention that are based on the 2-5-8 compositions (a=2, b=0, c=5 and d=8), such as Sr2Si5N8:RE, are as follows.
REx′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8 for Red and Other Phosphors
In one embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8, (note that this formula may be rewritten in the format of the general formula, M(x/v)(M′aM′′b)Si(c−x)AlxNd:RE, as Ca0.5x(Cax′′Sr1−x′′)2−x′Eux′Si5−xAlxN8, similarly all formulas provided herein may be rewritten in this format) wherein 0.1≦x≦1.3, 0.00001≦x′≦0.2, and 0≦x′′≦1, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula Eux′(Cax′′Sr(1−x′′))(2+0.5−x′)Si(5−x)AlxN8 is more narrowly represented wherein 0.3≦x≦1.3, 0.0001≦x′≦0.1, and 0.05≦x′′≦0.4, more narrowly wherein 0.5≦x≦1.3, 0.001≦x′≦0.1, and 0.1≦x′′≦0.3, and more narrowly wherein 0.7≦x≦1.3, for example, wherein 1.0≦x≦1.3 or wherein 1.05≦x≦1.25.
The nitride-based compounds of the phosphor may have a crystalline structure with a single phase or a mixed phase and include a 2-5-8 phase in pure or mixed form. The nitride-based compounds described herein distinguish previous nitride phosphors having a 1-1-1-3 phase or CASN phase (e.g., CaSiAlN3)—which generally have the space group Cmc21. Generally, the crystalline structures of the 2-5-8 nitride-based compounds as described herein have a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof. In some examples, the space group is Pmn21.
In embodiments described herein, the phosphors are enabled to emit a fluorescent light at a desired or predetermined wavelength when irradiated with an excitation source. (Herein an excitation source is typically a blue excitation source having a wavelength ranging from about 420 nm to about 470, although the excitation source may have a wider range from about 250 nm to about 420 nm; a common blue excitation source is a InGaN LED, or GaN LED, emitting with a peak wavelength of about 460 nm.) The phosphor containing Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8 is generally enabled to emit a red fluorescent light, although the phosphor is also enabled to emit a fluorescent light of other colors. The fluorescent light emitted by the phosphor containing Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8 may have a peak emission wavelength within a range from about 600 nm to about 675 nm under an excitation wavelength within a range from about 400 nm to about 480 nm. In some examples, the peak emission wavelength is within a range from about 610 nm to about 640 nm, more narrowly within a range from about 620 nm to about 625 nm. In other examples, the peak emission wavelength is within a range from about 630 nm to about 660 nm, more narrowly within a range from about 640 nm to about 655 nm.
In another embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula REx′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlXN8, wherein RE is at least one element selected from Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof, 0.1≦x≦3, 0.00001≦x′≦0.2, and 0≦x′′≦1, and the nitride-based compound has a crystalline structure having a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites. A phosphor activator is represented by M which contains one element, two elements, or more elements for activating the nitride-based compound of the phosphor. In some examples, the phosphor activator contains Eu and at least one or more elements. Therefore, the M is Eu and one or more elements selected from Ce, Pr, Nd, Sm, Gd, Th, Dy, Ho, Er, Tm, Yb, or combinations thereof. In some examples, the chemical formula REx′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8 is more narrowly represented wherein 0.3≦x≦2.5, 0.0001≦x′≦0.1, and 0≦x′′≦1, more narrowly wherein 1≦x≦2, 0.001≦x′≦0.1, and 0.05≦x′′≦0.4, more narrowly wherein x=2, 0.001≦x′≦0.1, and 0.1≦x′′≦0.3.
In another embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8, wherein 0.1≦x≦3, 0.00001≦x′≦0.2, and 0≦x′′≦1, and the nitride-based compound has a crystalline structure having a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula Eux′(Cax′′Sr(1−x′))(2+0.5x−x′)Si(5−x)AlxN8 is more narrowly represented wherein 0.5≦x≦2.5, 0.0001≦x′≦0.1, and 0≦x′′≦1, more narrowly wherein 1≦x≦2, 0.001≦x′≦0.1, and 0.05≦x′′≦0.4, and more narrowly wherein x=2, 0.001≦x′≦0.1, and 0.1≦x′′≦0.3. In other examples, the chemical formula Eux′(Cax′′Sr(1−x′′))(2+0.5x−x′)Si(5−x)AlxN8 is more narrowly represented wherein 0.1≦x≦1.3, 0.0001≦x′≦0.1, and 0.05≦x′′≦0.4, and more narrowly wherein 0.5≦1.3, 0.001≦x′≦0.1, and 0.1≦x′′≦0.3.
In another embodiment, a phosphor (e.g., a red phosphor) containing a nitride-based compound is represented by the chemical formula Eux′(Cax′′Sr(1−x′′))(3−x′)Si3Al2N8, wherein 0.00001≦x′≦0.2, and 0≦x′′≦1, and the nitride-based compound has a crystalline structure having a space group selected from Pmn21, Cc, derivatives thereof, or mixtures thereof, Al substitutes for Si within the crystalline structure, and the Ca charge balance cations are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula Eux′(Cax′′Sr(1−x′′))(3−x′)Si3Al2N8 is more narrowly represented wherein 0.0001≦x′≦0.1, and 0.05≦x′′≦0.4, more narrowly wherein 0.001≦x′≦0.1, and 0.1≦x′′≦0.3, and more narrowly wherein 0.001≦x′≦0.1, and 0.1≦x′′≦0.3.
FIG. 1 depicts an emission spectra of Eu:Ca(2+0.5x)Si(s−x)AlxN8 with different x values, as described by embodiments herein. When the value of x increases, the emission peak shifts to longer wavelength. The emission peak intensity drops first, then increases with the increasing x value to reach the highest intensity when x=2.5. Therefore, the phosphor with the chemical formula Eu:Ca3.25Si2.5Al2.5N8 has the highest intensity which approaches the intensity of Eu:CaAlSiN3 phosphor. The phosphor with the chemical formula Eu:Ca3.25Si2.5Al2.5N8 contains 2.5 moles of silicon, 2.5 moles of aluminum, and 3.25 moles of calcium.
FIGS. 2A-2B depict emission spectra of Eu0.05(SrxCa(1−x))2.95Si3Al2N8, with different x values, as described by embodiments herein. FIG. 2B shows plots of peak emission wavelength and corresponding photoluminescent intensity as a function of x. The highest intensity for Eu0.05(SrxCa(1−x))2.95Si3Al2N8 is when x=0.8, having a Sr/Ca ratio of about 4, while the next highest is when x=0.6, having a Sr/Ca ratio of about 1.5. The peak wavelength shifts to shorter wavelengths with an increasing Sr concentration.
FIGS. 3A-3B depict emission spectra of Eux(Sr0.8Ca0.2)3−xSi3Al2N8, with varying Eu concentrations (different x values). FIG. 3A depicts the emission spectra prior to exposing the phosphor to a sintering process while FIG. 3B depicts the emission spectra of the phosphor subsequent to being sintered in a nitride furnace at about 1,700° C. for about 7 hours. As the Eu concentration increases, the emission peak shifts to a longer wavelength. In FIG. 3A, the peaks for Eu=0.03 and 0.015 have the highest intensity and the lowest Eu concentration, respectively. After being sintered, as depicted in FIG. 3B, all of the spectra for different Eu concentrations have almost identical PL intensities. FIG. 3C depicts XRD patterns of Eux(Sr0.8Ca0.2)3−xSi3Al2N8 at the different x values (or Eu concentrations) subsequent to being sintered in a nitride furnace at about 1,700° C. for about 7 hours. As expected, FIG. 3C shows that Eu doping at these low levels does not affect the crystal structure of the phosphor.
Some specific embodiments of the present invention that are based on the alpha silicon nitride compositions (a=0, b=0, c=3 and d=4), such as Si3N4:RE, are as follows.
REx′Ca(0.5x−x′)Si(3−x)AlxN4 for Orange and Other Phosphors
In another embodiment, a phosphor (e.g., an orange phosphor) containing a nitride-based compound is represented by the chemical formula REx′Ca(0.5x−x′)Si(3−x)AlxN4, wherein RE is at least one element selected from Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof, 0.1<x<3, and 0.0001≦x′≦0.2, and wherein said nitride-based compound has the general crystalline structure of α-Si3N4 (i.e. an α-Si3N4 structure), Al substitutes for Si within said crystalline structure, and the Ca atoms are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula REx′Ca(0.5x−x′)Si(3−x)AlxN4 is more narrowly represented wherein 0.1<x<3 and 0.0001≦x′≦0.2, more narrowly wherein 0.2≦x≦2 and 0.001≦x′≦0.1, more narrowly wherein 0.3≦x≦1.8 and 0.005≦x′≦0.1, and more narrowly wherein 0.3≦x≦1.8 and x′=0.03.
In many examples, the phosphor contains a nitride-based compound represented by the chemical formula Eux′Ca(0.5x−x′)Si(3−x)AlxN4, wherein 0.3≦x≦1.8 and 0.005≦x′≦0.1, such as wherein 0.3≦x≦1.8 and x′=0.03, and wherein said nitride-based compound has the general crystalline structure of α-Si3N4, Al substitutes for Si within said crystalline structure, and the Ca atoms are located within the crystalline structure substantially at the interstitial sites. In other examples, the nitride-based compound is represented by the chemical formula Eu0.03Ca(0.5x)Si(3−x)AlxN4, wherein 0.1<x<3, and wherein said nitride-based compound has the general crystalline structure of α-Si3N4, Al substitutes for Si within said crystalline structure, and the Ca atoms are located within the crystalline structure substantially at the interstitial sites. In some examples, the phosphor activator contains Eu and at least one or more elements. Therefore, the RE is Eu and one or more elements selected from Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof.
The phosphor containing REx′Ca(0.5x−x′)Si(3−x)AlxN4 is generally enabled to emit an orange fluorescent light when irradiated with an excitation source, although the phosphor is also enabled to emit a fluorescent light of other colors. The fluorescent light emitted by the phosphor containing REx′Ca(0.5x−x′)Si(3−x)AlxN4 may have a peak emission wavelength within a range from about 570 nm to about 680 nm under an excitation wavelength within a range from about 400 nm to about 480 nm. In some examples, the peak emission wavelength is within a range from about 580 nm to about 620 nm, more narrowly within a range from about 590 nm to about 600 nm. In other examples, the peak emission wavelength is within a range from about 590 nm to about 670 nm, more narrowly within a range from about 650 nm to about 670 nm.
Table 1 includes data from emission spectra of Ca((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03, with different x values, as described by embodiments herein. Note that Ca((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03, which is equivalent to Eu0.03Ca(0.5x−0.03)Si(3−x)AlxN4 if the x values listed in Table 1 are multiplied by 3. FIG. 4 depicts emission spectra of Ca((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03, with different x values, as specified in Table 1. Table 2 includes data from emission spectra of Eu0.025Ca0.44Si2.07Al0.93N4, as described by embodiments herein. Table 2 includes samples identified with “7 h” and “14 h”—this refers to 7 hours and 14 hours of sintering, respectively, at a temperature of about 1,700° C. in a nitride furnace. It is apparent from the data that the longer sintering time improves the photoluminescence intensity (and the crystallinity) of the phosphor. Table 2 also specifies two different sources of Eu—EuCl3 and EuF3. The EuCl3 appears to improve the PL intensity and shift the peak to shorter wavelength.







TABLE 1







Ca((3x/2)−0.03)(Si1−xAlx)3N4Eu0.03












Sample

Peak wavelength





#
x
(nm)
PL
CIEx
CIEy





154
0.10
592
0.89
0.522
0.473


153
0.20
599
0.97
0.546
0.451


150
0.25
598
1.05
0.547
0.450


162
0.30
599
1.09
0.554
0.443


171
0.40
652
0.70
0.592
0.406


172
0.50
663
1.09
0.637
0.362


173
0.60
663
1.54
0.688
0.312
















TABLE 2







Ca0.44(Si0.69Al0.31)3N4Eu0.025
















Peak








wavelength


D50V


Sample #
Eu type
PL
(nm)
CIEx
CIEy
(μm)†
















213-175-7h
EuCl3
1.22
595.79
0.554
0.444
3.71


214-175-7h
EuF3
1.07
598.96
0.566
0.433
4.62


213-175-14h
EuCl3
1.27
595.62
0.553
0.445
5.56


214-175-14h
EuF3
1.13
599.17
0.565
0.433
6.10





†D50V is the median particle size of the cumulative volume distribution.






REx′Sr(0.5x−x′)Si(3−x)AlxN4 for Green and Other Phosphors

In another embodiment, a phosphor (e.g., a green phosphor) containing a nitride-based compound is represented by the chemical formula REx′Sr(0.5x−x′)Si(3−x)AlxN4, wherein RE is at least one element selected from Eu, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof, 0.1<x<3, and 0.0001≦x′≦0.2, and wherein said nitride-based compound has the general crystalline structure of α-Si3N4, Al substitutes for Si within said crystalline structure, and the Sr atoms are located within the crystalline structure substantially at the interstitial sites. In some examples, the chemical formula REx′Sr(0.5x−x′)Si(3−x)AlxN4 is more narrowly represented wherein 0.1<x<3 and 0.0001≦x′≦0.2, more narrowly wherein 0.2≦x≦2 and 0.001≦x′≦0.1, more narrowly wherein 0.3≦x≦1.8 and 0.005≦x′≦0.1, and more narrowly wherein 0.3≦x≦1.8 and x′=0.03.
In many examples, the phosphor contains a nitride-based compound represented by the chemical formula Eux′Sr(0.5x−x′)Si(3−x)AlxN4, wherein 0.3≦x≦1.8 and 0.005≦x′≦0.1, such as wherein 0.3≦x≦1.8 and x′=0.03, and wherein said nitride-based composition has the general crystalline structure of α-Si3N4, Al substitutes for Si within said crystalline structure, and the Sr atoms are located within the crystalline structure substantially at the interstitial sites. In other examples, the nitride-based compound is represented by the chemical formula Eu0.03Sr(0.5x)Si(3−x)AlxN4, wherein 0.1<x<3, and wherein said nitride-based composition has the general crystalline structure of α-Si3N4, Al substitutes for Si within said crystalline structure, and the Sr atoms are located within the crystalline structure substantially at the interstitial sites. In some examples, the phosphor activator contains Eu and at least one or more elements. Therefore, the RE is Eu and one or more elements selected from Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or combinations thereof.
The phosphor containing REx′Sr(0.5x−x′)Si(3−x)AlxN4 is generally enabled to emit a green fluorescent light when irradiated with an excitation source, although the phosphor is also enabled to emit a fluorescent light of other colors. The fluorescent light emitted by the phosphor containing REx′Sr(0.5x−x′)Si(3−x)AlxN4 may have a peak emission wavelength within a range from about 530 nm to about 670 nm under an excitation wavelength within a range from about 400 nm to about 480 nm. In some examples, the peak emission wavelength is within a range from about 530 nm to about 650 nm, more narrowly within a range from about 540 nm to about 595 nm. In other examples, the peak emission wavelength is within a range from about 600 nm to about 670 nm, more narrowly within a range from about 625 nm to about 650 nm.
Table 3 includes data from emission spectra of Sr((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03 with different x values, as described by embodiments herein. Note that Sr((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03, which is equivalent to Eu0.03Sr(0.5x−0.03)Si(3−x)AlxN4 if the x values listed in Table 3 are multiplied by 3. FIG. 5 depicts emission spectra of Sr((3x/2)−0.03)(Si(1−x)Alx)3N4Eu0.03, with different x values, as specified in Table 3.







TABLE 3







Sr((3x/2)−0.03)(Si1−xAlx)3N4Eu0.03














Sample

Peak wavelength






#
x
(nm)
PL
CIEx
CIEy







183
0.5
634
0.36
0.639
0.361



182
0.4
640
0.47
0.577
0.414



184
0.3
545
0.69
0.426
0.543



181
0.2
566
0.39
0.447
0.508



180
0.1
590
0.41
0.481
0.487










Exemplary Method for Forming Phosphors

In one embodiment, the raw materials Ca3N2, AlN, Si3N4, and EuX3 (X=Cl or F) are sealed within an inert atmosphere such as nitrogen and/or argon, and maintained in such a state using a glove box. The raw materials are then weighed within the inert atmosphere, usually in a glove box, and then mixed using ordinary methods known in the art, including mixing with either a mortar or ball mill. The resulting mixture is placed in a crucible, which is then transferred to a tube furnace or a high-pressure furnace connected directly to the glove box. This is so that exposure of the mixed raw materials to an inert atmosphere is maintained. In the furnace, the mixed raw materials are heated to a temperature of about 1,400° C. to about 1,700° C. using a heating rate of about 10° C. per minute, and maintained at that temperature for a time anywhere from about 2 to about 12 hours. The sintered product is cooled to room temperature, and pulverized using known methods, including mortar, ball mill, and the like, to produce a powder with the desired composition.
Exemplary synthesis processes for related nitride phosphors that may be helpful while fabricating the phosphors described herein are further disclosed in the commonly assigned U.S. application Ser. No. 12/250,400, filed Oct. 13, 2008 and published as U.S. Pub. No. 2009/0283721, which is herein incorporated by reference.
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.

## Claims

1. A nitride-based phosphor comprising calcium, silicon, aluminum, nitrogen and europium, wherein said nitride-based composition has the general crystalline structure of α-Si3N4, and Al substitutes for Si within said crystalline structure, and wherein said nitride-based phosphor absorbs radiation at a wavelength ranging from about 400 nm to about 480 nm and emits light with a photoluminescence peak emission wavelength within a range from about 592 nm to about 663 nm, wherein said nitride-based phosphor has a composition represented by the chemical formula Ca(1.5x−0.03)(Si(1−x)Alx)3N4Eu0.03, where x satisfies 0.1≦x≦0.6, and calcium is located within said crystalline structure substantially at the interstitial sites.

2. The nitride-based phosphor of claim 1, wherein said orange-red nitride-based phosphor emits light having CIE(x) coordinates ranging from 0.522 to 0.688 and CIE(y) coordinates ranging from 0.473 to 0.312.

3. A nitride-based phosphor comprising strontium, silicon, aluminum, nitrogen and europium, wherein said nitride-based composition has the general crystalline structure of α-Si3N4, and Al substitutes for Si within said crystalline structure, and wherein said nitride-based phosphor absorbs radiation at a wavelength ranging from about 400 nm to about 480 nm and emits light with a photoluminescence peak emission wavelength within a range from about 545 nm to about 640 nm, wherein said nitride-based phosphor has a composition represented by the chemical formula Sr(1.5x−0.03)(Si(1−x)Alx)3N4Eu0.03, where x satisfies 0.1≦x≦0.4, and strontium is located within said crystalline structure substantially at the interstitial sites.

4. The nitride-based phosphor of claim 3, wherein said nitride-based phosphor emits light having CIE(x) coordinates ranging from 0.426 to 0.577 and CIE(y) coordinates ranging from 0.543 to 0.414.