This nonprovisional application is based on Japanese Patent Application No. 2008-263136 filed on Oct. 9, 2008 with the Japan Patent Office, the entire contents of which are hereby incorporated by reference.
1. Field of the Invention
The present invention relates to a semiconductor light-emitting device including a semiconductor light-emitting element and phosphors as well as an image display and a liquid crystal display each employing the same.
2. Description of the Background Art
The competition for developing a backlight for a miniature liquid crystal display (LCD) has recently been intensified. While various systems of backlight sources are proposed in this field, no system simultaneously satisfying brightness and color reproducibility (NTSC ratio) has not yet been found. The NTSC ratio denotes the ratio of the area of a triangle obtained by connecting the chromaticity coordinates (u′, v′) of red, green and blue on a CIE1976 chromaticity diagram to the area of a triangle obtained by connecting the chromaticity coordinates (u′, v′) ((0.498, 0.519), (0.076, 0.576) and (0.152, 0.196)) of red, green and blue on the CIE1976 chromaticity diagram set by NTSC (National Television System Committee).
At present, a light-emitting device emitting white light formed by combining a light-emitting element (peak wavelength: about 450 nm) emitting blue light and a wavelength transformation portion employing a trivalent cerium-activated (Y,Gd)3(Al,Ga)5O12 phosphor or a bivalent europium-activated (Sr,Ba,Ca)2SiO4 phosphor excited by the blue light to emit yellow light is mainly employed as the backlight source for an LCD. When this light-emitting device is employed as the backlight for the LCD, however, color reproducibility (NTSC ratio) of the LC remains at about 70%.
For example, Japanese Patent Laying-Open No. 2004-287323 describes an RGB-LED formed by integrating a red LED chip, a green LED chip and a blue LED chip into a package and a structure obtained by combining an LED emitting ultraviolet light and an RGB phosphor with each other as backlights employing light-emitting diodes (LEDs). While the former can implement an NTSC ratio exceeding 100%, it is difficult to produce a desired color due to different driving characteristics of the LEDs, and the RGB-LED is unsuitable to a mobile device due to complicated driving circuits. The latter includes no blue phosphor having high brightness and suitable for a backlight.
Japanese Patent Laying-Open No. 2006-016413 discloses a light-emitting device emitting white light by exciting Eu-activated CaAlSiN3 which is a nitride-based phosphor emitting red light and a phosphor emitting green light with a light-emitting element emitting blue light. According to this system, a blue LED can be used as the light-emitting element emitting blue light, and hence the aforementioned problem of the absence of the blue phosphor having high brightness and suitable for a backlight can be solved. An Eu-activated β-sialon phosphor according to Japanese Patent Laying-Open No. 2005-255895, for example, has generally been suitably used as the phosphor emitting green light. The phosphors described in Japanese Patent Laying-Open Nos. 2006-016413 and 2005-255895 are based on silicon nitride-based ceramics stable against chemical and mechanical shocks, and hence a light-emitting device superior in environmental resistance and excellent in color stability can be implemented with these phosphors. When the light-emitting device emitting white light is formed by combining the green and red phosphors with the blue LED, wider color reproducibility (NTSC ratio) can be implemented as compared with the aforementioned case of employing the trivalent cerium-activated (Y,Gd)3(Al,Ga)5O12 phosphor or the bivalent europium-activated (Sr,Ba,Ca)2SiO4 phosphor emitting yellow light.
When the light-emitting device emitting white light with the blue LED and the red and green phosphors is employed as the backlight source of an image display such as a liquid crystal display, the color reproduction range of the display tends to widen if any of the phosphors has a small emission spectral width. When the blue LED and the phosphors described in Japanese Patent Laying-Open Nos. 2006-016413 and 2005-255895 are employed, the color reproduction range of red is insufficient since the red phosphor has an emission spectral width of at least 80 nm. Therefore, awaited are a semiconductor light-emitting device, emitting white light, capable of implementing a display showing deeper red and an image display employing the semiconductor light-emitting device emitting white light.
The present invention has been proposed in order to solve the aforementioned problems, and an object thereof is to provide a semiconductor light-emitting device capable of implementing a display capable of showing deeper red than ever with a semiconductor light-emitting element and phosphors and an image display employing the same.
The semiconductor light-emitting device according to the present invention includes a semiconductor light-emitting element emitting excitation light, a green phosphor and a red phosphor, and includes an Mn4+-activated phosphor as the red phosphor.
An Mn4+-activated phosphor having an emission peak wavelength of at least 625 nm and an emission spectral half width of not more than 30 nm can be suitably employed as the Mn4+-activated phosphor in the present invention.
The aforementioned Mn4+-activated phosphor is preferably Mn4+-activated Mg fluorogermanate or Mn4+-activated K2MF6 (M=Si, Ge or Ti).
A green phosphor having an emission peak wavelength of at least 510 nm and not more than 550 nm and an emission spectral half width of not more than 55 nm can be suitably employed as the green phosphor in the present invention.
An Eu-activated β-sialon phosphor or an Mn-activated γ-AlON phosphor can be suitably employed as the green phosphor in the present invention.
According to the present invention, the emission peak wavelength of the semiconductor light-emitting element is preferably 430 to 460 nm, more preferably 440 to 450 nm.
The present invention also provides an image display and a liquid display each including the aforementioned semiconductor light-emitting device emitting white light as a backlight source.
According to the present invention, a semiconductor light-emitting device capable of implementing a display capable of showing deeper red than ever when applied to an image display such as a liquid crystal display can be provided.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
<Red Phosphor>
In the Mn4+-activated phosphor employed as the red phosphor in the semiconductor light-emitting device according to the present invention, the emission spectral peak wavelength thereof is preferably at least 625 nm, and the emission spectral half width thereof is preferably not more than 30 nm. When the emission spectral peak wavelength of the red phosphor is at least 625 nm and the emission spectral half width thereof is not more than 30 nm, the red phosphor emits red light in a deep region. When the red phosphor emits red light in a deep region, a display showing deep red can be implemented when the semiconductor light-emitting device according to the present invention is applied to an image display such as a liquid crystal display. An Mn4+-activated Mg fluorogermanate phosphor illustrated in William M. Yen and Marvin J. Weber, “INORGANIC PHOSPHORS”, p. 212 (4.10 Miscellaneous Oxides, SECTION 4: PHOSPHOR DATA) published by CRC Press or an Mn4+-activated K2MF6 (M=Si, Ge or Ti) phosphor illustrated in Journal of the Electrochemical Society: SOLID-STATE SCIENCE AND TECHNOLOGY, July 1973, p. 942 can be listed as a preferable specific example of such an Mn4+-activated phosphor. An Mn4+-activated phosphor having an emission peak wavelength of at least 625 nm and an emission spectral half width of not more than 30 nm is suitably employed as the Mn4+-activated phosphor.
The Mn4+-activated Mg fluorogermanate phosphor is efficiently excited by blue light of 400 to 460 nm, and has a sharp emission spectral half width of 15 nm and an emission peak wavelength of 659 nm. The Mn4+-activated Mg fluorogermanate phosphor exhibits deep red with an emission spectral chromaticity point of (u′, v′)=(0.569, 0.513) on a CIE1976 chromaticity diagram. The Mn4+-activated K2MF6 (M=Si, Ge or Ti) phosphor is efficiently excited by blue light of 400 to 460 nm, and has a sharp emission spectral half width of 8 nm and an emission peak wavelength of 631 nm. The Mn4+-activated K2MF6 (M=Si, Ge or Ti) phosphor exhibits deep red with an emission spectral chromaticity point of (u′, v′)=(0.535, 0.520) on the CIE1976 chromaticity diagram.
<Green Phosphor>
When the aforementioned Mn4+-activated phosphor is regarded a first phosphor, semiconductor light-emitting device 1 according to the present invention preferably further includes a second phosphor emitting green light upon irradiation with the excitation light. In other words, while semiconductor light-emitting element 2 emits blue light and the aforementioned Mn4+-activated phosphor emits red light in semiconductor light-emitting device 1 according to the present invention, a green phosphor is preferably employed as the second phosphor, in order to obtain semiconductor light-emitting device 1 emitting white light by mixing the blue light and the red light. In semiconductor light-emitting device 1 according to the example shown in
The second phosphor employed for semiconductor light-emitting device 1 according to the present invention is preferably formed by a green phosphor emitting green light having a peak wavelength in the wave range of 510 to 550 nm upon irradiation with the excitation light. If the peak wavelength of the second phosphor is out of the aforementioned range, wavelength consistency with the color filters shown in
According to the present invention, the emission spectral half width of the second phosphor is preferably not more than 55 nm, more preferably not more than 45 nm, so that the image display shows deeper green when the semiconductor light-emitting device is applied to the image display.
An Eu-activated β-sialon phosphor or an Mn-activated γ-AlON phosphor shown in the pamphlet of International Patent Laying-Open No. 2007/099862 and Summaries of 68th Scientific Lectures of the Japan Society of Applied Physics, p. 1473, “Emission Characteristics of Aluminum Oxynitride Green Phosphor” can be suitably employed as such a second phosphor (green phosphor). Further, an Eu-activated β-sialon phosphor having a smaller emission spectral half width and a shorter peak wavelength shown in International Patent Laying-Open No. 2007/066733 can be more suitably employed.
When the aforementioned Eu-activated β-sialon phosphor and the Eu-activated CaAlSiN3 phosphor described in Japanese Patent Laying-Open No. 2006-016413 employed as the red phosphor are combined with each other to constitute the light-emitting device, the emission spectra of the green phosphor and the red phosphor so remarkably overlap with each other that the color reproduction range is narrowed when the light-emitting device is applied to an image display. According to the present invention, however, the Mn4+-activated phosphor such as the Mn4+-activated Mg fluorogermanate phosphor or the Mn4+-activated K2MF6 (M=Si, Ge or Ti) phosphor is employed as the red phosphor, whereby the problem of the overlap between the spectra of the red and green phosphors can be solved. This is because the emission spectral half width of the red phosphor employed in the present invention is narrower as compared with the Eu-activated CaAlSiN3 phosphor.
On the other hand, the fluorescent life times of the aforementioned Mn-activated γ-AlON phosphor and the Mn4+-activated phosphor employed as the red phosphor in the present invention were measured. As a result, the fluorescent life times of the Mn-activated γ-AlON phosphor and the Mn4+-activated phosphor, particularly the Mn4+-activated Mg fluorogermanate phosphor, were 4 msec. and 3 msec. respectively, and the afterglow times of the Mn-activated γ-AlON phosphor and the Mn4+-activated phosphor were at the same order. When an image display is prepared with the Mn-activated γ-AlON phosphor and the Mn4+-activated phosphor, therefore, influence exerted by the afterglow time on images can be easily controlled.
<Molding Resin>
In semiconductor light-emitting device 1 according to the present invention, molding resin 5 employed for sealing semiconductor light-emitting element 2 is prepared by dispersing a phosphor into translucent resin such as silicone resin or epoxy resin, and this phosphor includes the Mn4+-activated phosphor which is the aforementioned red phosphor (and the second phosphor (green phosphor) as the case may be). In this case, a phosphor mixture containing the green phosphor in addition to the red phosphor can be suitably employed as the dispersed phosphor, and a blue phosphor may be further added thereto if necessary. The mixing ratio of the dispersed phosphor is not particularly restricted but properly decided so that a spectrum exhibiting a desired white point is obtained on a screen when semiconductor light-emitting device 1 is applied to an image display and the color filters are fully opened, for example.
<Semiconductor Light-Emitting Element>
Semiconductor light-emitting element 2 employed for semiconductor light-emitting device 1 according to the present invention, which can be prepared from a semiconductor light-emitting element well known in the art, preferably emits primary light having an emission peak wavelength of 430 to 460 nm. If the emission peak wavelength of semiconductor light-emitting element 2 is out of the aforementioned range, the luminous efficiency of the red phosphor is reduced when the Mn4+-activated Mg fluorogermanate phosphor or the Mn4+-activated K2MF6 (M=Si, Ge or Ti) phosphor is employed as the Mn4+-activated phosphor, for example. A semiconductor light-emitting layer having an InGaN layer as an active layer can be preferably listed as a semiconductor light-emitting element exhibiting such an emission peak wavelength. The emission peak wavelength of semiconductor light-emitting element 2 employed in the present invention is more preferably 440 to 450 nm, to attain excellent wavelength consistency with a blue color filter described later.
<Printed Wiring Board>
A heat-resistant glass epoxy film or an insulating film can be employed as printed wiring board 3 employed in semiconductor light-emitting device 1 according to the present invention.
<p-Side Electrode>
A material such as Pd/Au, ITO (indium-tin oxide) or Ni can be employed from the side of active layer 6 as the structure of p-side electrode 8.
<n-Side Electrode>
Hf/Al, Ti/Al, Ti/Mo or Hf/Au can be employed from the side of active layer 6 as the structure of n-side electrode 7.
<n Electrode Portion>
Al or the like can be employed for n electrode portion 9.
<Image Display>
The present invention also provides an image display employing the aforementioned semiconductor light-emitting device according to the present invention emitting white light as a backlight source.
<Liquid Crystal Display>
As shown in
As shown in
While the present invention is now described in more detail with reference to Examples and comparative examples, the present invention is not restricted to these.
A powder aggregate having a composition of 50.884 mass % of magnesium oxide powder, 11.187 mass % of magnesium fluoride powder, 1.660 mass % of magnesium carbonate powder and 36.269 mass % of germanium oxide powder was obtained by weighing prescribed quantities of these materials and mixing the materials with each other for at least 10 minutes with a mortar and a pestle of silicon nitride sintered bodies. This powder aggregate was introduced into a crucible of boron nitride having a diameter of 20 mm and a height of 20 mm by gravity-drop, and the crucible was covered with a lid of boron nitride. Then, the crucible was set in a pressurized electric furnace of a graphite resistance heating system, heated to a temperature of 1200° C. and held at 1200° C. for 2 hours, to obtain a phosphor sample. The obtained phosphor sample was pulverized with a pestle of agate, to obtain phosphor powder. Then, the phosphor powder was reheated. The phosphor powder was introduced into the crucible of boron nitride having the diameter of 20 mm and the height of 20 mm by gravity-drop. Then, the crucible was set in the electric furnace of the graphite resistance heating system, heated to 1200° C. and held at the temperature for 16 hours, to obtain a phosphor sample. The obtained phosphor sample was pulverized with the pestle of agate, to obtain phosphor powder. When the phosphor powder was subjected to powder X-ray diffraction measurement (XRD) with Kα rays of Cu, all charts obtained from the phosphor powder exhibited an Mn4+-activated Mg fluorogermanate structure. The phosphor powder was irradiated with light having a wavelength of 365 nm emitted from a lamp, to confirm that the same emitted red light.
An n-type Si substrate was dipped in a solution of KMnO4:H2O:HF=3 g:50 cc:50 cc for 10 minutes, to obtain a crystal on the surface of the n-type Si substrate. Phosphor powder was obtained by separating the obtained crystal from the Si substrate, washing and filtrating the same. When the phosphor powder was subjected to powder X-ray diffraction measurement (XRD) with Kα rays of Cu, all charts obtained from the phosphor powder exhibited an Mn4+-activated K2SiF6 structure. The phosphor powder was irradiated with light having a wavelength of 365 nm emitted from a lamp, to confirm that the same emitted red light.
A powder aggregate having a composition of 95.82 mass % of α-type silicon nitride powder, 3.37 mass % of aluminum nitride powder and 0.81 mass % of europium oxide powder was obtained by weighing prescribed quantities of these materials and mixing the materials with each other for at least 10 minutes with a mortar and a pestle of silicon nitride sintered bodies. This powder aggregate was introduced into a crucible of boron nitride having a diameter of 20 mm and a height of 20 mm by gravity-drop.
Then, the crucible was set in a pressurized electric furnace of a graphite resistance heating system, into which nitrogen having purity of 99.999 volume % was introduced to set the pressure to 1 MPa, thereafter heated at 500° C. per hour up to 1900° C. and held at the temperature for 8 hours, to obtain a phosphor sample. The obtained phosphor sample was pulverized with a mortar of agate, to obtain phosphor powder. When the phosphor powder was subjected to powder X-ray diffraction measurement (XRD) with Kα rays of Cu, all charts obtained from the phosphor powder exhibited a β-sialon structure. The phosphor powder was irradiated with light having a wavelength of 365 nm emitted from a lamp, to confirm that the same emitted green light.
A powder aggregate, excellent in fluidity, having a composition of 95.20 mass % of silicon powder passed through a sieve of 45 μm, 4.55 mass % of aluminum nitride powder and 0.26 mass % of europium oxide powder was obtained by weighing prescribed quantities of these materials, mixing the materials with each other for at least 10 minutes with a mortar and a pestle of silicon nitride sintered bodies and thereafter passing the mixture through a sieve of 250 μm. This powder aggregate was introduced into a crucible of boron nitride having a diameter of 20 mm and a height of 20 mm by gravity-drop. Then, the crucible was set in an electric furnace of a graphite resistance heating system, into which nitrogen having purity of 99.999 volume % was introduced to set the pressure to 0.5 MPa, thereafter heated at 500° C. per hour up to 1300° C., thereafter heated at 1° C. per minute up to 1600° C. and held at the temperature for 8 hours, to obtain a phosphor sample. The obtained phosphor sample was pulverized with a mortar of agate, to obtain phosphor powder. The phosphor powder was subjected to powder X-ray diffraction measurement (XRD) with Kα rays of Cu. Consequently, all charts obtained from the phosphor powder exhibited a β-sialon structure. Then, the powder was reheated. The powder fired at 1600° C. was pulverized with the mortar and the pestle of silicon nitride sintered bodies, and thereafter introduced into the crucible of boron nitride having the diameter of 20 mm and the height of 20 mm by gravity-drop. Then, the crucible was set in the electric furnace of the graphite resistance heating system, into which nitrogen having purity of 99.999 volume % was introduced to set the pressure to 1 MPa, thereafter heated at 500° C. per hour up to 1900° C. and held at the temperature for 8 hours, to obtain a phosphor sample. The obtained phosphor sample was pulverized with the mortar of agate, to obtain phosphor powder. When the phosphor powder was subjected to powder X-ray diffraction measurement (XRD) with Kα rays of Cu, it was recognized that the phosphor powder had a β-sialon structure. The phosphor powder was irradiated with light having a wavelength of 365 nm emitted from a lamp, to confirm that the same emitted green light.
In order to synthesize a material consisting of Al7O9N containing 1 mol % of Mn, which is AlON of a theoretical composition, a powder aggregate having a composition of 13.2 mass % of aluminum nitride powder, 85.3 mass % of aluminum oxide powder and 1.5 mass % of manganese carbonate powder was obtained by weighing prescribed quantities of these materials and mixing the materials with each other for at least 10 minutes with a mortar and a pestle of silicon nitride sintered bodies. This powder aggregate was introduced into a crucible of boron nitride having a diameter of 20 mm and a height of 20 mm by gravity-drop.
Then, the crucible was set in a pressurized electric furnace of a graphite resistance heating system, into which nitrogen having purity of 99.999 volume % was introduced to set the pressure to 0.5 MPa, thereafter heated at 500° C. per hour up to 1800° C. and held at the temperature for 2 hours, to obtain a phosphor sample. The obtained phosphor sample was pulverized with a mortar of agate, to obtain phosphor powder. When the phosphor powder was subjected to powder X-ray diffraction measurement (XRD) with Kα rays of Cu, all charts obtained from the phosphor powder exhibited a γ-AlON structure. The phosphor powder was irradiated with light having a wavelength of 365 nm emitted from a lamp, to confirm that the same emitted green light.
A powder aggregate having a composition of 29.741 mass % of aluminum nitride powder, 33.925 mass % of α-type silicon nitride powder, 35.642 mass % of calcium nitride powder and 0.692 mass % of europium nitride powder was obtained by weighing prescribed quantities of these materials and mixing the materials with each other for at least 10 minutes with a mortar and a pestle of silicon nitride sintered bodies. Europium nitride was synthesized by nitriding metal europium in ammonia. The powder aggregate was introduced into a crucible of boron nitride having a diameter of 20 mm and a height of 20 mm by gravity-drop. All of the steps of weighing the materials, mixing the same with each other and molding the mixture were carried out in a glove box capable of maintaining a nitrogen atmosphere having a moisture content of not more than 1 ppm and an oxygen content of not more than 1 ppm.
Then, the crucible was set in a pressurized electric furnace of a graphite resistance heating system, into which nitrogen having purity of 99.999 volume % was introduced to set the pressure to 1 MPa, thereafter heated at 500° C. per hour up to 1800° C. and held at 1800° C. for 2 hours to obtain phosphor powder. When the phosphor powder was subjected to powder X-ray diffraction measurement (XRD) with Kα rays of Cu, it was recognized that the phosphor powder had the structure of a CaAlSiN3 crystal. The phosphor powder was irradiated with light having a wavelength of 365 nm emitted from a lamp, to confirm that the same emitted red light.
A semiconductor light-emitting device 1 having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device 1 having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device 1 having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device 1 having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device 1 having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device 1 having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device having the structure shown in
An image display having the structure shown in
A semiconductor light-emitting device having the structure shown in
An image display having the structure shown in
[Results of Evaluation]
Table 1 shows NTSC ratios and chromaticity coordinates of white, red, green and blue points of light components shown on screens of the image displays according to Examples 2, 4, 6, 8, 10 and 12 and comparative examples 2, 4 and 6 on CIE1976 chromaticity diagrams. The red, green and blue points denote chromaticity points on the displays in a case of displaying only light components transmitted through red, green and blue color filters respectively, and the white points denote chromaticity points on the displays in a case of fully opening all color filters. The chromaticity points and the NTSC ratios shown in Table 1 were measured with MCPD-2000 by Otsuka Electronics Co., Ltd.
It is understood from Table 1 that the green and red points show deeper chromaticness in the image displays according to Examples 2, 4, 6, 8, 10 and 12 as compared with those according to comparative examples 2, 4 and 6. This is because the Mn4+-activated Mg fluorogermanate phosphor according to preparation example 1 and the Mn4+-activated K2SiF6 phosphor according to preparation example 2 emit light in deeper red and have sharper emission spectral half widths as compared with the Eu-activated CaAlSiN3 (CASN) phosphor according to comparative preparation example 1. Comparing Examples 2 and 4 and Examples 8 and 10 with each other in particular, it is understood that the image displays according to Examples 4 and 10 show deeper green. This is because the β-sialon phosphor according to preparation example 4 emits deeper green light as compared with the β-sialon phosphor according to preparation example 3.
Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the scope of the present invention being interpreted by the terms of the appended claims.
Number | Date | Country | Kind |
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2008-263136(P) | Oct 2008 | JP | national |