JP2007214579A - Phosphor conversion light emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light emitting device having desired color rendering properties. <P>SOLUTION: A phosphor conversion light emitting device includes a light emitting layer disposed between n-type region and a p-type region, so as to emit light having a first peak wavelength; a first phosphor constituted so as to emit light having a second peak wavelength; a second phosphor constituted so as to emit light having a third peak wavelength. The second phosphor is a phosphor activated by Eu3+, constituted so that a maximum intensity in a wavelength range from 460 to 470 nm is at least 5% of the maximum intensity in the wavelength range from 220 to 320 nm, in an excitation spectrum in 298 K and 1.013 bar. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a phosphor-converted semiconductor light emitting device.

  Among the most efficient light sources, semiconductor light emitting devices, including light emitting diodes (LEDs), resonator LEDs (RCLEDs), vertical cavity surface emitting laser diodes (VCSELs), and edge emitting lasers are now available. Yes. Material systems currently of interest in the fabrication of high-intensity light-emitting devices that can operate over the visible spectrum include III-V semiconductors, specifically gallium, aluminum, indium and so-called III-nitride materials. Includes certain binary, ternary and quaternary alloys of nitrogen. Typically, group III nitride light-emitting devices are fabricated on metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), or sapphire, silicon carbide, group III nitride, or other suitable substrates. Other epitaxial techniques are produced by epitaxially growing stacks of semiconductor layers of various compositions and dopant concentrations. The stack includes one or more n-type layers, for example doped with silicon, formed on a substrate, one or more light-emitting layers in an active region formed on the n-type layer, Often includes one or more p-type layers, for example doped with magnesium, formed over the active region. Electrical contacts are formed on the n-type region and the p-type region.

  Since the light emitted by currently available group III-nitride devices is generally at shorter wavelengths in the visible spectrum, the light generated by group-III nitride devices produces light with longer wavelengths. Can be easily converted. Light having a first peak wavelength (“primary light”) is light having a longer peak wavelength (“secondary light”) using a process known as luminescence / fluorescence. Is known in the art. The fluorescence emission process includes absorbing the primary light by a wavelength converting material such as a phosphor and exciting the luminescent center of the phosphor material that emits the secondary light. The peak wavelength of the secondary light depends on the phosphor material. The type of phosphor material can be selected to produce secondary light having a specific peak wavelength.

In a typical application, the light emitting device and phosphor material are selected such that the light combining the primary light and the secondary light appears white. In a typical white phosphor-converted LED, a group III nitride die that emits blue light is combined with a phosphor that emits yellow light, such as Y ₃ Al ₅ O ₁₂ : Ce ³⁺ . Such white light devices typically have undesirable color rendering properties because the combined light is lacking in the red region of the visible light spectrum.

  US Pat. No. 6,351,069 discloses a phosphor-converted LED comprising two phosphors, a first phosphor that emits yellow light and a phosphor that emits red light.

  According to various embodiments of the present invention, a phosphor-converted light emitting device includes a light emitting layer disposed between an n-type region and a p-type region and configured to emit light having a first peak wavelength. A semiconductor structure including: a first phosphor configured to emit light having a second peak wavelength; and a second phosphor configured to emit light having a third peak wavelength. Including. The second phosphor is such that, in the excitation spectrum at 298 K and 1.013 bar, the maximum intensity in the wavelength region between 460 nm and 470 nm is at least 5% of the maximum intensity in the wavelength region between 220 nm and 320 nm. It is a configured phosphor activated by Eu3 +.

Red-emitting phosphor activated by EU ²⁺ is labile to involuntary by the tendency of the EU ²⁺ that react with the other components present in the light emitting device is oxidized or the other components. Another disadvantage of phosphors activated by EU ²⁺ is a relatively broad emission band that causes low lumen volume (light flux).

Red-emitting phosphors activated by EU ³⁺ are generally more stable than EU ²⁺ activated phosphors over their lifetime, but phosphors activated by EU ³⁺ are generally In particular, it has strong absorption only at UV-C and VUV, which are very short wavelengths, but its absorption is very weak at longer wavelengths, especially at visible wavelengths. The weak absorptivity at long wavelengths makes water for such EU ³⁺ applications in phosphor-converted light emitting devices. This is because the emission wavelength of an efficient high-brightness LED used in such devices is generally higher than the wavelength region where such phosphors activated by EU ³⁺ have strong absorption. Because it is in the UV-A spectral region above 350 nm or in the blue spectral region, which is a significantly longer wavelength.

According to various embodiments of the present invention, a phosphor-converted light emitting device includes a red light emitting phosphor activated by EU ³⁺ having an excitation spectrum suitable for use with a blue light emitting LED. In some embodiments, in the excitation spectrum of a phosphor material activated by EU ³⁺ (298K, 1.013 bar), the maximum intensity in the wavelength region between 460 nm and 470 nm is between 220 nm and 320 nm. At least 5% of the maximum intensity in the wavelength region. As used herein, in the absorption spectrum, the term “intensity” refers to the amount of light absorbed (corresponding to absorption power).

In some embodiments, the red phosphor activated by EU ^3+, of the fluorescent body Eu atoms, at least 90%, more preferably at least 95%, more preferably at least 98%, EU ^{3 Take} the form of ⁺ . The spectral (absorption and emission) properties of EU ³⁺ materials are more stable than EU ²⁺ materials over time. This is because EU ³⁺ does not oxidize as easily as EU ²⁺ . Therefore, the fewer EU ²⁺ atoms, the better the lifetime effect of the phosphor material.

By using the improved absorption capability of the phosphor material activated by EU ³⁺ in the blue spectral region specified as described above, the light emitting device according to various embodiments of the present invention is an LED having blue primary color light. And can operate efficiently. The absorptive power of the conversion element depends on the absorption power of the material itself and the thickness of the conversion element in the propagation direction of the primary color light. In order to obtain an equivalent absorption power, the more efficient light conversion material (high absorption power of the material itself) according to various embodiments of the present invention allows the application of thinner phosphor materials for more compact devices. Enable and / or reduce the risk of secondary light reabsorption and the subsequent radiation-less transition, which leads to an improved efficiency of the light emitting device due to the thinner conversion elements. Improving the blue absorption capability will also improve the absorption capability near the UV-A region between 350 nm and 420 nm. Thus, in various embodiments of the present invention, the emission of LEDs in the UV-A region can be combined with phosphor materials according to various embodiments of the present invention.

In some embodiments, the peak region in the wavelength region between 680 nm and 720 nm is in the wavelength region between 570 nm and 720 nm in the emission spectrum (298K, 1.013 bar) of the phosphor material activated by EU ³⁺ At least 15% of the peak area at. Such devices exhibit deep red emission characteristics because an efficiency of 100-200 lumens / watt can be achieved for some applications. Such devices can also exhibit improved color points due to the stability of the red phosphor. As used herein, the term “peak area” refers to the total amount of light within a particular wavelength region.

In one embodiment of the present invention, the EU atomic dopant level in the phosphor material activated by EU ³⁺ is increased to 20% and comprises 20%. Higher EU ³⁺ concentrations lead to significant energy transitions of absorbed energy to the surface and defect sites, and thus a phenomenon known as concentration quenching, EU ³⁺ luminescence. It leads to quenching.

In one embodiment of the invention, the phosphor material activated by EU ³⁺ further comprises a group comprising bismuth (Bi), indium (In), thallium (Tl), antimony (Sb) or mixtures thereof. A plurality of co-dopant M selected from These additional dopants are elements having a large number of electrons on the d orbital, which increases the electron density and improves the absorption capacity of EU ³⁺ in the main lattice. In one embodiment of the present invention, the concentration of atomic dopants of M (atomic-%) in materials activated by EU ³⁺ is increased to 20%. ^Increasing the concentration of M ³⁺ leads to significant energy transitions to the absorbed light surface and defect sites, thus leading to quenching of activator luminescence.

In one embodiment of the invention, the ratio of EU (atomic-%) to M (atomic-%) in the material activated by EU ³⁺ is 0.1: 1 to 10: 1. In the above-mentioned ratio of Eu to M (Eu: M), when two or more kinds of dopants are present, M represents the sum of all the kinds of dopants.

In one embodiment of the invention, the phosphor material activated by EU ³⁺ is an oxide, oxyhalogenides, garnet, vanadate, tungstate, borate, silicate, germanium. It is selected from the group comprising acid salts or mixtures thereof. These materials result in high electron density at the oxygen anions defect sites in the main lattice, which leads to the improved absorption properties of EU ³⁺ .

In one embodiment of the invention, the phosphor material activated by EU ³⁺ is (Gd _{1 -xz} Lu _x ) ₂ O ₃ : Eu _z , (Y _{1 -xz} Gd _x Lu _y ) ₃ Al ₅ O ₁₂ : Eu _z , Ba ₂ (Y _1-xyz Gd _x Lu _y ) ₂ Si ₄ O ₁₃ : Eu _z , Ba ₂ (Y _1-xyz Gd _x Lu _y ) ₂ Ge ₄ O ₁₃ : Eu _z , (Y _1-xyz Gd _x Lu _y ) VO ₄ : Eu _z , (Y _1-xyz Gd _x Lu _y ) OF: Eu _z , (Y _1-xyz Gd _x Lu _y ) OCl: Eu _z , Ba (Y _1-xyz Gd _x Lu _y ) B ₉ O ₁₆ : Eu _z , Ba ₃ (Y _1-xyz Gd _x Lu _y ) (BO ₃ ) ₃ : Eu _z , (Y _1-xyz Gd _x Lu _y ) ₂ SiO ₅ : Eu _z , (Ca _1-a Sr _a ) ₃ (Y _1-xyz Lu _w Ga _x In _y ) ₂ Ge ₃ O ₁₂ : Eu _z (a, w, x, y = 0.0-1.0, z = 0.0-0.2), (Ca _1-a Sr _a ) ₃ (Y _1-xyz Lu _v Ga _W In _x ) ₂ Ge ₃ O ₁₂ : Eu _y Bi _z (a, v, w, x = 0.0-1.0, y, z = 0.0- 0.2), LaOM with M = (Br, Cl, I): Eu, Na ₉ [(Y _1-xyz Lu _x Gd _y ) W ₁₀ O ₃₆ ]: Eu _z , (Y _1-xyz Lu _x Gd _y ) [P (Mo ₃ O ₁₀ ) ₄ ]: Eu _z (x, y = 0.0-1.0, z = 0.0-0.2) and a mixture thereof. Here, EU ³⁺ is surrounded by ions with a high negative charge density, which leads to improved absorption properties in the vicinity of UV-A and the blue spectral region.

  The light emitting device according to the present invention can be used in a wide variety of systems and / or applications, including one or more of the following systems. Systems include office lighting systems, home application systems, shop lighting systems, home lighting systems, accent lighting systems, spot lighting systems, theater lighting systems, fiber optic application systems, projection systems, self-illuminating display systems, pixelated display systems, segments Display systems, warning sign systems, medical lighting application systems, indicator sign systems, decorative lighting systems, portable systems, automotive applications and green house lighting systems.

  The components described above are subject to any special exceptions regarding size, shape, material selection and technical concepts, as well as the components recited in the claims and components used in accordance with various embodiments of the invention. The selection criteria known in the relevant field can be applied without limitation.

1 and 2 show the excitation and emission spectra of a Y ₂ O ₃ : Eu material with a 5% Eu doping level. The absorption of Eu ^{3+ in} the UV-C and VUV spectral regions is strong but very weak below the low energy edge of the charge transition state around 300 nm. This weak absorption at wavelengths greater than 300 nm prevents the Eu ³⁺ phosphor having the spectrum as shown in FIGS. 1 and 2 from being applied to a phosphor-converted light emitting diode. This is because the minimum emission wavelength for an efficient high-brightness LED is generally at least 370 nm outside the strong absorption wavelength region of the Y ₂ O ₃ : Eu phosphor material. The ^{_{395nm (7 F 0 - 5 D}} 3) and ^{_{465nm (7 F 0 - 5 D}} 2) absorption lines around is spin forbidden 4f-4f transitions, therefore, a very weak absorption lines.

Red line emitting EU ³⁺ phosphor according to various embodiments of the present invention, a relatively strong absorption and / or _{^{395nm (7 F 0 - 5 D}} 3) of UV-A radiation and 465nm ⁽⁷ F ₀ - ⁵ D ₂ ) Has a blue emission due to the improvement of weak absorption lines around. This is because the use of a grating having a high covalency or the host lattice ^{[Ar] 3d 10, [Kr} ] 4d 10, is more doped with ions having an [Xe] 4f ¹⁴ 5d ¹⁰ electronic structure ( This is achieved by co-doping). By applying covalent valence lattices or multiple dopants rich in electrons, the spin-forbidden properties of Eu ³⁺ 4f-4f transitions are relaxed to some extent, which is the absorption of these transitions. Strength will be increased. This improved absorption property effectively applies these materials as color converters for organic or inorganic state-of-the-art light emitting diodes with emission wavelengths in the UV-A and / or blue spectral region It is possible to do.

A suitable Eu-containing phosphor material for improving absorption according to the present invention is (Gd _1-x Lu _x ) ₂ O ₃ : Eu, (Y _1-y Gd _x Lu _y ) ₃ Al ₅ O ₁₂ : Eu, Ba ₂ (Y _1-xy Gd _x Lu _y ) ₂ Si ₄ O ₁₃ : Eu, Ba ₂ (Y _1-xy Gd _x Lu _y ) ₂ Ge ₄ O ₁₃ : Eu, (Y _1-xy Gd _x Lu _y ) VO ₄ : Eu, (Y _1-xy Gd _x Lu _y ) OF: Eu _z , (Y _1-xy Gd _x Lu _y ) OCl: Eu, Ba (Y _1-xy Gd _x Lu _y ) B ₉ O ₁₆ : Eu, Ba ₃ (Y _1-xy Gd _x Lu _y ) (BO ₃ ) ₃ : Eu, (Y _1-xy Gd _x Lu _y ) ₂ SiO ₅ : Eu, (Ca _1-a Sr _a ) ₃ (Y _1-wxyz Lu _w Ga _x In _y ) ₂ Ge ₃ O ₁₂ : Eu _z (a, w, x, y = 0.0-1.0, z = 0.0-0.2), (Ca _1-a Sr _a ) ₃ (Y _1-wxyz Lu _v Ga _W In _x ) ₂ Ge ₃ O ₁₂ : Eu _y Bi _z (a, v, w, x = 0.0-1.0, y, z = 0.0-0.2), M = (Br, Cl , I) and high covalent lattices such as LaOM: Eu and mixtures thereof. Here, Eu ³⁺ is surrounded by ions having a high negative charge density. The preferred Eu doping level is increased to 20% atoms. Within these materials, Eu ³⁺ exhibits a strong covalent interaction with the main lattice that affects the transition probabilities of spin-forbidden transitions compared to atomic transition probabilities.

Covalent valence interactions with the main lattice of Eu ³⁺ can cause multiple main lattices with other triple positively charged ions such as Bi ³⁺ , In ³⁺ , Tl ³⁺ Sb ³⁺ or mixtures thereof. It is further enhanced by seed doping. The preferred level of doping multiple In3 + is increased to 10% atoms. According to another embodiment of the present invention, the atomic dopant level of M in the phosphor material containing Eu is increased to 5%. According to another embodiment of the present invention, the atomic dopant level of M in the phosphor material containing Eu is increased to 1%.

  According to one embodiment of the present invention, the atomic% ratio of Eu to M in the phosphor material containing Eu is between 0.5: 1 and 5: 1. According to one embodiment of the present invention, the atomic% ratio of Eu to M in the phosphor material containing Eu is 1: 1 to 3: 1. When two or more multi-type dopants M are present, the term M in the above ratio indicates the sum of all multi-type dopants.

The absorbed excitation energy is generally relaxed by secondary radiation having a longer wavelength. Prior to radiation relaxation (electron transition from the excited state to the ground state), the excited D level relaxes the non-radiative state to the excited D ground state ⁵ D ₀ . According to the transition rule, the transition to the ⁷ F ₂ state is allowed, but the transition to the ⁷ F ₄ state that leads to deep red emission is forbidden by spin. In order to increase the light efficiency and the color rendering ratio, deep red light emission having a wavelength around 700 nm is preferable. The high electron density of the phosphor material containing Eu ^{3+ according} to the invention is also improved compared to the transition ⁵ D _0- > ⁷ F ₂ where the spin forbidden transition ⁵ D _0- > ⁷ F ₄ is allowed. Affect the light emission characteristics.

The examples described below show improved absorption and emission properties of phosphor materials containing Eu ^{3+ according} to various embodiments of the present invention. For a clear comparison with the phosphors shown in FIGS. 1 and 2, the example described below includes the same Eu doping level of 5 atomic% Eu ³⁺ . The presence of Eu ³⁺ is predetermined by the material preparation. The person skilled in the art knows what starting material should be selected to prepare a material containing essentially Eu ³⁺ .

(Example 1)
3 and 4 show the excitation and emission spectra of LaOCl: Eu. In FIG. 3, the maximum intensity in the wavelength region between 460 nm and 470 nm is about 21% of the maximum intensity in the wavelength region between 220 nm and 320 nm. In FIG. 4, the peak region in the wavelength region between 680 nm and 720 nm is 22% of the peak region in the wavelength region between 570 nm and 720 nm.

(Example 2)
5 and 6 show the excitation and emission spectra of Sr ₃ In ₂ Ge ₃ O ₁₂ : Eu. In FIG. 5, the maximum intensity in the wavelength region between 460 nm and 470 nm is about 25% of the maximum intensity in the wavelength region between 220 nm and 320 nm. In FIG. 6, the peak region in the wavelength region between 680 nm and 720 nm is 25% of the peak region in the wavelength region between 570 nm and 720 nm.

(Example 3)
7 and 8 show the excitation and emission spectra of Y ₂ SiO ₅ : Eu. In FIG. 7, the maximum intensity in the wavelength region between 460 nm and 470 nm is about 11% of the maximum intensity in the wavelength region between 220 nm and 320 nm. In FIG. 8, the peak region in the wavelength region between 680 nm and 720 nm is 21% of the peak region in the wavelength region between 570 nm and 720 nm.

(Fig. 4)
9 and 10 show excitation and emission spectra of Ca ₃ Ga ₂ Ge ₃ O ₁₂ : Eu. In FIG. 9, the maximum intensity in the wavelength region between 460 nm and 470 nm is about 11% of the maximum intensity in the wavelength region between 220 nm and 320 nm. In FIG. 10, the peak region in the wavelength region between 680 nm and 720 nm is 27% of the peak region in the wavelength region between 570 nm and 720 nm.

  According to one embodiment of the present invention, the maximum intensity in the wavelength region between 460 nm and 470 nm in the excitation spectrum (298 K, 1.013 bar) of the phosphor material containing Eu is the same as in Examples 3 and 4 above. As indicated, at least about 11% of the maximum intensity in the wavelength region between 220 nm and 320 nm.

  According to another embodiment of the present invention, in the excitation spectrum (298K, 1.013 bar) of the phosphor material containing Eu, the maximum intensity in the wavelength region between 460 nm and 470 nm is between 220 nm and 320 nm. At least about 15% of the maximum intensity in the wavelength region.

  According to one embodiment of the present invention, in the excitation spectrum (298 K, 1.013 bar) of the phosphor material containing Eu, the maximum intensity in the wavelength region between 460 nm and 470 nm is the same as in Examples 1 and 2 above. As indicated, at least about 20% of the maximum intensity in the wavelength region between 220 nm and 320 nm.

  According to one embodiment of the present invention, in the excitation spectrum (298K, 1.013 bar) of the phosphor material containing Eu, the peak region in the wavelength region between 680 nm and 720 nm is the above-described Example 1, Example 2, As shown for Examples 3 and 4, it is at least 20% of the peak region in the wavelength region between 570 nm and 720 nm. Other phosphor materials including Eu can exhibit different peak area ratios.

(Example 5)
FIG. 11 shows an emission spectrum according to one embodiment of the present invention. The LED was manufactured as follows. A powder mixture of 20% (Y, Gd) _{3 Al 5} O ₁₂ : Ce and 80% Y ₂ SiO ₅ : Eu was suspended in the liquid silicone precursor compound. The drop of silicone precursor was placed on an LED die emitting light with a wavelength of 465 nm, after which the silicone was polymerized. The LED was then sealed using a plastic lens. As FIG. 11 shows, the resulting LED shows good optical properties with a _Tc of 3000K.

(Example 6)
FIG. 12 shows the emission spectrum of an LED according to one embodiment of the present invention. The LED was manufactured as follows. A powder mixture of 20% (Y, Gd) ₃ A ₁₅ O ₁₂ : Ce and 80% LaOCl: Eu was suspended in the liquid silicone precursor compound. The drop of silicone precursor was placed on an LED die emitting light with a wavelength of 465 nm, after which the silicone was polymerized. The LED was then sealed using a plastic lens. As FIG. 12 shows, the resulting LED shows good optical properties with a _Tc of 3100K.

  In other embodiments, an Eu doping level different from 5 atomic% can be selected, for example, to adapt the size of the conversion element and the spectral characteristics of the conversion element to the desired application.

  The specific combinations of elements and features in the various embodiments described above are merely exemplary, and it is also explicitly intended that these techniques be replaced and replaced with other techniques. . Those skilled in the art will appreciate that variations, modifications, and other implementations of what is disclosed herein do not depart from the spirit and scope of the invention as defined in the claims. You can recognize that this is something that can be considered by the contractor. Accordingly, the above disclosure is illustrative and not intended to be limiting. The technical scope of the present invention is defined by the claims and their equivalents. Furthermore, reference signs used in the present specification and claims do not limit the technical scope of the invention described in the claims.

(Materials and methods)
The spectrum of the material containing Eu according to the present invention was measured using an on-site built spectrum spectrofluorometer. The light source for this spectrofluorometer system is a 150 W xenon (Xe) lamp in an air-cooled housing. The lamp output was focused on the entrance slit of the excitation monochromator (Bentham) using a 0.5 m focal length. The light exiting from the exit slit of this excitation monochromator is sent into the sample chamber and is focused on the sample material to be tested through several mirrors. The sample to be tested is oriented in the horizontal direction, but the optical axes of the excitation and emission branches are oriented in the vertical direction and are approximately parallel. This geometric orientation ensures reliable quantitative comparative measurements for various samples. The sample chamber is optically coupled to a light emitting monochromator (Bentham, focal length 0.5 m) via a mirror system. Detection of the emitted light is performed using a thermo-electrically cooled photomultiplier tube (PMT) unit mounted in the exit slit of the light emitting monochromator. This system is entirely controlled by a computer by a DOS-based software program based on DOS.

The sample to be tested is formed as a powder layer having a thickness of 2 mm, and the spot size of the excitation light beam is approximately ² × ³ mm ² . The spectral resolution of the excitation and emission branches is on the order of 1-2 nm. A 1 nm step size was selected for determination of excitation and emission spectra.

The red light-emitting phosphor activated by Eu ³⁺ described above is particularly effective for use in a phosphor-converted LED configured to emit white light. In such a device, a blue light emitting LED can be combined with a yellow or green light emitting phosphor and a red light emitting Eu3 + activated phosphor, or a UV light emitting LED can be combined with a blue light emitting phosphor, Yellow or green emitting phosphors can be combined with phosphors activated by red emitting Eu3 +.

Suitable yellow or green-emitting phosphors have the general formula (Lu _1-xyab Y _x Gd _y ) ₃ (Al _1-z Ga _z ) ₅ O ₁₂ : Ce _a Pr _b (where 0 <x <1, 0 < y <1, 0 <z ≦ 0.1, 0 <a ≦ 0.2, 0 <b ≦ 0.1), for example including SrGa ₂ S ₄ : Eu ²⁺ and Sr _1-x Ba _x SiO ₄ : Eu ²⁺ Lu ₃ Al ₅ O ₁₂ : Ce ³⁺ , Y ₃ Al ₅ O ₁₂ : Ce ³⁺ , SrSi ₂ N ₂ O ₂ : Eu ²⁺ , (Sr _1-uvx Mg _u Ca _v Ba _x ) (Ga _2-yz Al _y In _z S ₄ ): including aluminum garnet phosphors such as Eu ²⁺ . Suitable blue emitting phosphors include, for example, MgSrSiO ₄ .

The red phosphor activated by Eu ³⁺ described above can provide advantages over other red phosphors. First, the excitation spectrum of a red phosphor activated by Eu ³⁺ is usually limited to a sharp line (ie, a narrow wavelength region) in the visible spectrum, as shown in FIGS. Thus, the red phosphor activated by Eu ³⁺ does not absorb the light emitted by either the yellow or green light emitting phosphor in the device. As a result, a red phosphor activated by Eu ^3+, there is no need to separate from the yellow or green-emitting phosphor, a white light phosphor converted LED comprising a red phosphor activated by Eu ³⁺ Can provide significant flexibility in implementation. Second, the color rendering of white light in a device containing a red phosphor activated by Eu ³⁺ is a linear emission from the red phosphor (ie, narrow, as shown in FIGS. 4, 6, 8 and 10). (Wavelength region). For example, in some embodiments, the combined light emitted from such a device has a corrected color temperature (CCT) between 2800K and 3300K, with a color rendering ratio Ra between 80 and 87 Can have.

  FIG. 13 is a cross-sectional view showing a portion of a device that includes a blue light emitting LED combined with a yellow or green phosphor formed as a luminescent ceramic and a red phosphor activated by Eu3 + as described above. In the device shown in FIG. 13, a group III semiconductor structure 18 including at least one light emitting layer 20 disposed between an n-type region and a p-type region is grown on a growth substrate (not shown). A portion of the semiconductor structure 18 is etched to expose regions of each conductivity type so that p and n contacts are formed on the same surface of the device, and the device is mounted as a flip chip. It has become.

  The semiconductor structure 18 is connected to a mount 12, which can be ceramic or silicon based, for example, by metal interconnects 14 and 16, which are connected to the mount 12. Are connected to a p-contact and an n-contact (not shown) in the semiconductor structure 18. The growth substrate can remain as part of the device (placed between the semiconductor structure 18 and the luminescent ceramic 22) or can be removed from the semiconductor structure. One or both of the p-contact and the n-contact are reflective to the light generated by the light emitting layer 20, and a semiconductor structure 18 in which most of the light emitted from the semiconductor structure is oriented as shown in FIG. Can be allowed to exit through the upper surface.

A yellow or green emitting phosphor in the form of a luminescent ceramic 22 is disposed on the upper surface of the semiconductor structure 18. Luminescent ceramics are described in detail in US Patent Application Publication No. 2005-0269582, the contents of which are incorporated herein by reference. A suitable Y ₃ Al ₅ O ₁₂ : Ce ³⁺ ceramic can be made as follows. That is, 40 g of Y ₂ O ₃ (99.998%), 32 g of Al ₂ O ₃ (99.999%) and 3.44 g of CeO ₂ were mixed with 1.5 kg of high-purity alumina balls in isopropanol on a roller bench for 12 hours. (2mm diameter) After this, the dried precursor is roasted at 1300 degrees Celsius for 2 hours in a CO environment. The resulting YAG powder is then deagglomerated using a planet ball mill (agate ball) under ethanol. The ceramic abrasive is then slip cast to obtain a ceramic green body after drying. This green body is then sintered between the graphite plates for 2 hours at 1700 degrees Celsius.

  The luminescent ceramic 22 is applied to the semiconductor structure 18 by, for example, direct wafer bonding, or an organic material such as epoxy, acrylic or silicone, one or more high refractive index inorganic materials, or sol-gel glass. Can be attached by adhesive.

  High refractive index materials include, for example, high refractive index optical glasses such as Schott glass SF59, Schott glass LaSF 3, schott glass LaSF N18, and mixtures thereof. These glasses are available from Schott Glass Technologies Incorporated, Drier Pennsylvania. Other high refractive index materials include, for example, (1) high refractive index chalcogenide glass such as (Ge, Sb, Ga) (S, Se) chalcogenide glass, (2) GaP, InGaP, GaAs and GaN. III-V group semiconductors including, but not limited to, (3) II-VI group semiconductors including, but not limited to, ZnS, ZnSe, ZnTe, CdS, CdSe and CdTe, (4) Si and Ge limited to these Group IV semiconductors and compounds including without (5) organic semiconductors, (6) tungsten oxide, titanium oxide, nickel oxide, zirconium oxide, indium tin oxide, metal oxides including without limitation chromium oxide, ( 7) Metal fluorides including but not limited to magnesium fluoride and calcium fluoride, (8) Metals including but not limited to Zn, In, Mg and Sn, (9) Yttrium aluminum garnet ( YAG), (9) phosphide compound, (10) arsenide compound, (11 ) Antimonide compounds, (12) nitride compounds, (13) high refractive index organic compounds, and (14) mixtures or alloys thereof. Adhesion using high refractive index inorganic materials is described in detail in US Pat. No. 7,053,419, the contents of which are incorporated herein by reference.

Solgel glass is described in detail in US Pat. No. 6,642,618, the contents of which are incorporated herein by reference. In embodiments such as luminescent ceramic is attached by Sorugerugarasu the semiconductor structure or the growth substrate, closely to the refractive index of the surface of the semiconductor structure the refractive index of SiO ₂ Sorugerugarasu refractive index and luminescent ceramic luminescent ceramic is attached One or more materials, such as titanium, cerium, lead, gallium, bismuth, cadmium, zinc, barium or aluminum oxides, are added to the SiO ₂ sol-gel glass to increase the refractive index of the sol-gel glass for matching. Can be included.

  The luminescent glass is woven, cast, ground, machined, hot stamped, and shaped into the desired shape, for example, to increase light extraction. For example, a luminescent ceramic is formed as a lens, such as a dome lens or a Fresnel lens, roughened, or woven using a photonic crystal structure such as a periodic grid of holes formed in the ceramic. . The formed ceramic layer can be smaller than the surface to which it is attached, can be the same size as this surface, or it can be larger than this surface.

  A mount 12 that supports the semiconductor structure 18 and the luminescent ceramic 22 is placed in the reflective cup 10, after which a second phosphor layer 24 is placed on the luminescent ceramic. The second phosphor layer 24 is activated by one or more red phosphors, which are activated by Eu3 + as described above, placed in a transparent adhesive material 26 such as resin, silicone or epoxy. Particles 28) including at least one red-emitting phosphor.

FIG. 14 is a cross-sectional view showing a portion of a device including a blue light emitting LED coupled to a yellow or green light emitting phosphor formed as a separate luminescent ceramic layer and a red light emitting phosphor activated by Eu ³⁺ . is there. As shown in FIG. 13, a group III nitride semiconductor structure including a light emitting region configured to emit blue light is mounted on a mount 12. A yellow or green light emitting phosphor in the form of a luminescent ceramic 22 is disposed on the upper surface of the semiconductor structure 18. A red-emitting phosphor activated by Eu ^{3+ in} the form of a luminescent ceramic 30 is arranged on the upper surface of the luminescent ceramic 22. The luminescent ceramics 30 and 22 can be connected to each other, for example, by direct wafer bonding, as described above, or by organic materials such as epoxy, acrylic or silicone, one or more high refractive index inorganic materials, or sol-gel glass. It is connected by such an adhesive. The position of the luminescent ceramics 30 and 22 relative to the semiconductor structure 18 can also be reversed. The luminescent ceramics 30 and 22 can each have a thickness between 100 μm and 300 μm.

The red-emitting phosphor activated by Eu ³⁺ will allow this powder phosphor material to remain until the particles of the powder phosphor material begin to form a strong bond or neck at the contact point of the particle. By heating, it can be formed as a luminescent ceramic. The temperature and pressure at which sintering occurs may depend on the specific phosphor material used. During sintering, the partially bonded particles form a strong agglomeration that further reduces its porosity by further neck growth. Grain boundaries are formed that move so that some grains grow at the expense of other grains. This stage of sintering continues while the pore channels are bonded (open porosity) until the pores are separated (closed porosity). In the final stage of sintering, the plurality of pores are closed and gently removed along the grain boundaries until the desired degree of densification is achieved.

FIG. 15 is a cross-sectional view illustrating a portion of a device including a blue light emitting LED coupled to a yellow or green light emitting phosphor formed as a regular layer and a red light emitting phosphor activated by Eu ³⁺ . . In the device shown in FIG. 15, a yellow or green light emitting phosphor is formed as a regular layer 32 on the top of the growth substrate 34, the side surface of the growth substrate 34, and the side surface of the semiconductor structure 18. Regular phosphor layer 32 may be formed, for example, by stenciling as described in US Pat. No. 6,650,044 or as described in US Pat. No. 6,576,488. It can be formed by electrophoretic deposition. Both US Pat. No. 6,650,044 and US Pat. No. 6,576,488 are hereby incorporated by reference. As in FIG. 13, as described above, it includes one or more red phosphor particles 28, at least one red-emitting phosphor activated by Eu ³⁺ , such as a resin, silicone or epoxy. A phosphor layer 24, which is arranged with such a transparent adhesive material, is formed on the regular phosphor layer 32.

  FIG. 16 is an enlarged view showing the packaged light emitting device described in detail in US Pat. No. 6,274,924. A heat dissipation slug 100 is placed in an insert-molded lead frame. The insert-molded lead frame is, for example, a filled plastic material 105 molded around a metal frame 106 that provides an electrical path. The slug 100 can include an optional reflector cup 102. A light emitting device die 104, which can be any of the devices described in the various embodiments described above, is attached to the slag 100 directly to the slag 100 or via a thermally conductive mount 103. It is mounted indirectly. A cover 108 can be added which can be an optical lens.

  In various embodiments of the present invention, the LEDs and phosphors contained in a white device can be made to reach a desired range via a preferred set of color filters, for example when the device is used as a backlight for an RGB display. You can choose to achieve.

  Although the present invention has been described in detail, those skilled in the art will be able to make various modifications to the present invention based on the disclosure herein, without departing from the spirit of the invention described herein. Can be applied. Therefore, the technical scope of the present invention is not limited to the specific embodiments shown in this specification.

FIG. 1 is a diagram showing the excitation spectrum of a weak Y ₂ O ₃ : Eu material at wavelengths greater than 300 nm. FIG. 2 is a diagram showing an emission spectrum of the material of FIG. FIG. 3 is a diagram illustrating an excitation spectrum for a first example of a material containing Eu according to various embodiments of the present invention. FIG. 4 is a diagram showing an emission spectrum of the material of FIG. FIG. 5 is a diagram showing an excitation spectrum for a second example of a material containing Eu according to various embodiments of the present invention. FIG. 6 is a diagram showing an emission spectrum of the material of FIG. FIG. 7 is a diagram showing an excitation spectrum for a third example of a material containing Eu according to various embodiments of the present invention. FIG. 8 is a diagram showing an emission spectrum of the material of FIG. FIG. 9 is a diagram showing an excitation spectrum for a fourth example of a material containing Eu according to various embodiments of the present invention. FIG. 10 is a diagram showing an emission spectrum of the material of FIG. FIG. 11 is a diagram showing emission spectra of devices according to various embodiments of the present invention. FIG. 12 is a diagram showing emission spectra of devices according to various embodiments of the present invention. FIG. 13 is a diagram showing a device including an LED, a luminescent ceramic, and a phosphor disposed in a transparent layer. FIG. 14 shows a device including an LED and two luminescent ceramics. FIG. 15 is a diagram showing a device including an LED, a regular layer, and a phosphor disposed in a transparent layer. FIG. 16 is an enlarged view showing a packaged light emitting device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Cup 12 Mount 14,16 Metal interconnection 18 Semiconductor structure 22 Luminescent ceramic 24 2nd fluorescent substance layer 26 Adhesive material 28 Particle | grain 30 Luminescent ceramic 32 Conformal layer 34 Growth substrate

Claims (20)

a light emitting layer disposed between the n-type region and the p-type region and configured to emit light having a first peak wavelength; and
A first phosphor arranged in a path of light emitted by the light emitting layer and configured to emit light having a second peak wavelength;
A second phosphor disposed in a path of light emitted by the light emitting layer and configured to emit light having a third peak wavelength;
Comprising
The second phosphor comprises Eu ³⁺ ;
In the excitation spectrum of the second phosphor at 298 K and 1.013 bar, the maximum intensity in the wavelength region between 460 nm and 470 nm is at least 5% of the maximum intensity in the wavelength region between 220 nm and 320 nm Device characterized by.   The device of claim 1, wherein the semiconductor structure comprises a III-nitride structure. The first peak wavelength is blue;
The second peak wavelength is yellow or green;
The device of claim 1, wherein the third peak wavelength is red.   The device of claim 1, wherein the third peak wavelength is longer than the second peak wavelength.   The device of claim 1, wherein the first phosphor is formed on the semiconductor structure and the second phosphor is formed on the first phosphor.   The device of claim 1, wherein the first phosphor is disposed within a ceramic member.   The device of claim 6, wherein the second phosphor comprises a plurality of particles disposed in a transparent material disposed on the ceramic member.   The device of claim 6, wherein the ceramic member is a first ceramic member, and the second phosphor is disposed within the second ceramic member. The second ceramic member is disposed on the first ceramic member;
The device according to claim 8, wherein the first ceramic member and the second ceramic member are connected by an adhesive.   The device of claim 1, wherein the first phosphor is a regular layer disposed on top and sides of the semiconductor structure.   The device of claim 10, wherein the second phosphor comprises a plurality of particles disposed in a transparent material disposed over the conformal layer. The first phosphor is (Lu _1-xyab Y _x Gd _y ) ₃ (Al _1-z Ga _z ) ₅ O ₁₂ : Ce _a Pr _b (where 0 <x <1, 0 <y <1, 0 <z ≦ 0.1, 0 <a ≦ 0.2, 0 <b ≦ 0.1), Lu ₃ Al ₅ O ₁₂ : Ce ³⁺ , Y ₃ Al ₅ O ₁₂ : Ce ³⁺ , SrSi ₂ N ₂ O ₂ : Eu ^{2 _{+, (Sr 1-uvx Mg}} u Ca v Ba x) (Ga 2-yz Al y In z S 4): Eu 2+, SrGa 2 S 4: Eu 2+ and _{Sr 1-x Ba x SiO 4} : Eu The system of claim 1, wherein the system is one of ²⁺ .   In the emission spectrum of the second phosphor at 298 K and 1.013 bar, the peak region in the wavelength region between 680 nm and 720 nm is at least 15% of the peak region in the wavelength region between 570 nm and 720 nm. Item 2. The device according to Item 1.   The device of claim 1, wherein the atomic dopant level of Eu in the second phosphor material is 20% or less.   The device of claim 1, wherein the second phosphor further comprises a plurality of dopants comprising one of Bi, In, Tl, Sb, and mixtures thereof.   16. The device of claim 15, wherein the atomic percent ratio of Eu to the plurality of dopants in the second phosphor material is between 0.1: 1 and 10: 1.   The second phosphor is selected from the group comprising oxide, oxyhalide, garnet, vanadate, tungstate, borate, silicate, germanate, and mixtures thereof. Item 2. The device according to Item 1. The second phosphor is
(Gd _1-xz Lu _x ) ₂ O ₃ : Eu _z , (Y _1-xz Gd _x Lu _y ) ₃ Al ₅ O ₁₂ : Eu _z , Ba ₂ (Y _1-xyz Gd _x Lu _y ) ₂ Si ₄ O ₁₃ : Eu _z , Ba ₂ (Y _1-xyz Gd _x Lu _y ) ₂ Ge ₄ O ₁₃ : Eu _z , (Y _1-xyz Gd _x Lu _y ) VO ₄ : Eu _z , (Y _1-xyz Gd _x Lu _{y y} ) OF: Eu _z , (Y _1-xyz Gd _x Lu _y ) OCl: Eu _z , Ba (Y _1-xyz Gd _x Lu _y ) B ₉ O ₁₆ : Eu _z , Ba ₃ (Y _1-xyz Gd _x Lu _y ) (BO ₃ ) ₃ : Eu _z , (Y _1-xyz Gd _x Lu _y ) ₂ SiO ₅ : Eu _z , (Ca _1-a Sr _a ) ₃ (Y _1-xyz Lu _w Ga _x In _y ) ₂ Ge ₃ O ₁₂ : Eu _z (a, w, x, y = 0.0-1.0, z = 0.0-0.2), (Ca _1-a Sr _a ) ₃ (Y _1-xyz Lu _v Ga _W In _x ) ₂ Ge ₃ O ₁₂ : Eu _y Bi _z (a, v, w, x = 0.0-1.0, y, z = 0.0-0.2), LaOM with M = (Br, Cl, I): Eu, Na ₉ [( Y _1-xyz Lu _x Gd _y ) W ₁₀ O ₃₆ ]: Eu _z , (Y _1-xyz Lu _x Gd _y ) [P (Mo ₃ O ₁₀ ) ₄ ]: Eu _z (x, y = 0.0-1.0, 2. The device of claim 1, selected from the group comprising z = 0.0-0.2) and mixtures thereof.   The synthesized light emitted from the device is a part of the light emitted by the light emitting layer, a part of the light emitted by the first phosphor, and the light emitted by the second phosphor. The device of claim 1 having a corrected color temperature between 2800K and 3300K.   The synthesized light emitted from the device is a part of the light emitted by the light emitting layer, a part of the light emitted by the first phosphor, and the light emitted by the second phosphor. The device of claim 1, wherein the device has a color rendering ratio Ra between 80 and 87.

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