JP2008007734A - Light-emitting composition, light source device, display unit, and manufacturing method of light-emitting composition - Google Patents
Light-emitting composition, light source device, display unit, and manufacturing method of light-emitting composition Download PDFInfo
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本発明は、蛍光体を含む発光組成物と、この発光組成物を有する光源装置と、この光源装置によって構成される表示装置と、発光組成物の製造方法と、に関する。 The present invention relates to a luminescent composition containing a phosphor, a light source device having the luminescent composition, a display device including the light source device, and a method for manufacturing the luminescent composition.
蛍光体は、構成元素の種類やその組成比の選定によって、所望の波長帯で発光させることができる。
近年、蛍光体を用いた表示装置として、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬ（Electro Luminescence；電界発光）ディスプレイなどの、所謂ＦＰＤ（Flat Panel Display）と呼称される薄型の表示装置が開発され、研究も盛んに行われている。
The phosphor can emit light in a desired wavelength band by selecting the type of constituent elements and the composition ratio.
In recent years, thin display devices called so-called FPD (Flat Panel Display) such as liquid crystal displays, plasma displays, and organic EL (Electro Luminescence) displays have been developed and studied as display devices using phosphors. It is also actively performed.
これらの表示装置は、例えば液晶ディスプレイにおける液晶のような部材、つまり表示装置全体の分類の目安となる部材が設けられた光学装置を有する。そして、この光学装置に対し、例えばバックライトなどの形で、光源装置が設けられることにより、表示装置が構成される。
表示装置において、蛍光体は、光源装置に用いられる。そして、蛍光体を有する光源装置の中でも、青色光で励起される蛍光体と、青色光源となるＬＥＤ（Light Emitting Diode）との組み合わせによって白色ＬＥＤが構成された光源装置は、特に注目されている。
These display devices include, for example, an optical device provided with a member such as a liquid crystal in a liquid crystal display, that is, a member serving as a standard for classification of the entire display device. A display device is configured by providing a light source device in the form of a backlight or the like for the optical device.
In the display device, the phosphor is used for a light source device. Among light source devices having a phosphor, a light source device in which a white LED is configured by a combination of a phosphor excited by blue light and an LED (Light Emitting Diode) serving as a blue light source has attracted particular attention. .
しかしながら、青色光で励起される蛍光体の殆どは、耐湿性が低く、空気（雰囲気）中に含まれる水分によって特性が劣化してしまうという欠点を有している。
一般に、光源装置は、常温常湿にとどまらず、より厳しい条件下（例えば温度４０℃以上かつ湿度９０％ＲＨ（Relative Humidity）以上）での信頼性試験をクリアする必要がある。しかし、青色光で励起される蛍光体を有する光源装置の多くは、蛍光体の耐湿性が低いために、この信頼性試験をクリアすることができない。
However, most phosphors excited with blue light have low moisture resistance, and have the disadvantage that the characteristics deteriorate due to moisture contained in the air (atmosphere).
In general, a light source device is not limited to normal temperature and humidity, and needs to pass a reliability test under more severe conditions (for example, a temperature of 40 ° C. or higher and a humidity of 90% RH (Relative Humidity) or higher). However, many of the light source devices having a phosphor excited by blue light cannot pass this reliability test because the humidity resistance of the phosphor is low.
このような、蛍光体における耐湿性の問題に対し、蛍光体の表面にガラスを付着させることによって耐湿性の向上を図る手法が提案されている（例えば特許文献１参照）。
しかしながら、本発明者らは、ガラスを付着させても、蛍光体の耐湿性が充分に向上するとは限らないことを見出した。これは、粉体の表面にガラスを付着させる一般的な手法である液相法において、粉体の析出しやすい箇所に集中的にガラスが析出する一方で、析出しにくい箇所は殆どガラスで覆われず、付着箇所に偏りが生じるためと考えられる。
However, the present inventors have found that even when glass is adhered, the moisture resistance of the phosphor is not always improved sufficiently. This is because, in the liquid phase method, which is a general technique for attaching glass to the surface of the powder, the glass is intensively deposited on the portion where the powder is liable to precipitate, whereas the portion where the precipitation is difficult is covered with glass. This is thought to be due to the fact that the adhering location is biased.
本発明はこのような問題に鑑みてなされたものであって、その目的は、蛍光体の耐湿性向上が図られた発光組成物と、この発光組成物を有する光源装置と、この光源装置によって構成される表示装置と、発光組成物の製造方法と、を提供することにある。 The present invention has been made in view of such problems, and an object of the present invention is to provide a light emitting composition in which the moisture resistance of a phosphor is improved, a light source device having the light emitting composition, and the light source device. It is in providing the display apparatus comprised and the manufacturing method of a luminescent composition.
本発明に係る発光組成物は、蛍光体を含む発光組成物であって、上記蛍光体の表面の少なくとも一部が、保護層によって覆われ、上記保護層が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有することを特徴とする。 The light-emitting composition according to the present invention is a light-emitting composition containing a phosphor, wherein at least a part of the surface of the phosphor is covered with a protective layer, and the protective layer is made of nitrogen (N) or fluorine (F ) Including a first protective film.
本発明に係る光源装置は、第１発光組成物と、第２発光組成物と、青色光源と、を有する光源装置であって、上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、上記青色光源からの青色光によって励起される蛍光体を含み、上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、蛍光体の表面の少なくとも一部が、保護層によって覆われ、上記保護層が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有することを特徴とする。 The light source device according to the present invention is a light source device having a first light emitting composition, a second light emitting composition, and a blue light source, and among the first light emitting composition and the second light emitting composition, At least one includes a phosphor excited by blue light from the blue light source, and at least one of the first light emitting composition and the second light emitting composition has at least a part of the surface of the phosphor, The protective layer is covered with a protective layer, and the protective layer includes a first protective film containing nitrogen (N) or fluorine (F).
本発明に係る表示装置は、第１発光組成物と、第２発光組成物と、青色光源と、を有する光源装置と、この光源装置からの光に対して所定の変調を施し、所定の出力光を出力する光学装置と、を有する表示装置であって、上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、上記青色光源からの青色光によって励起される蛍光体を含み、上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、蛍光体の表面の少なくとも一部が、保護層によって覆われ、上記保護層が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有することを特徴とする。 A display device according to the present invention includes a light source device having a first light emitting composition, a second light emitting composition, and a blue light source, and applies predetermined modulation to light from the light source device, and outputs a predetermined output. An optical device that outputs light, wherein at least one of the first light-emitting composition and the second light-emitting composition is a phosphor excited by blue light from the blue light source. And at least one of the first light-emitting composition and the second light-emitting composition has at least a part of the surface of the phosphor covered with a protective layer, and the protective layer includes nitrogen (N) or fluorine ( A first protective film including F) is provided.
本発明に係る発光組成物の製造方法は、蛍光体の表面の少なくとも一部に、物理気相成長法によって、少なくとも窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を形成する第１保護膜形成工程を有することを特徴とする。 In the method for producing a luminescent composition according to the present invention, a first protective film containing at least nitrogen (N) or fluorine (F) is formed on at least a part of the surface of the phosphor by physical vapor deposition. It has a protective film forming step.
本発明に係る発光組成物によれば、蛍光体表面の少なくとも一部が、保護層によって覆われ、この保護層が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有することから、耐湿性の向上が図られる。 According to the light emitting composition according to the present invention, at least a part of the phosphor surface is covered with the protective layer, and this protective layer has the first protective film containing nitrogen (N) or fluorine (F). The moisture resistance is improved.
本発明に係る光源装置によれば、第１発光組成物及び第２発光組成物のうち少なくとも一方が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有する保護層によって蛍光体表面が覆われた構成を有することから、発光組成物の耐湿性向上によって、光源装置の長期信頼性の向上が図られる。 According to the light source device of the present invention, at least one of the first luminescent composition and the second luminescent composition has the phosphor surface by the protective layer having the first protective film containing nitrogen (N) or fluorine (F). Therefore, the long-term reliability of the light source device can be improved by improving the moisture resistance of the luminescent composition.
本発明に係る表示装置によれば、第１発光組成物及び第２発光組成物のうち少なくとも一方が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有する保護層によって蛍光体表面が覆われた構成を有することから、発光組成物の耐湿性向上によって、表示装置の長期信頼性の向上が図られる。 According to the display device of the present invention, at least one of the first light emitting composition and the second light emitting composition has a phosphor surface by a protective layer having a first protective film containing nitrogen (N) or fluorine (F). Thus, the long-term reliability of the display device can be improved by improving the moisture resistance of the luminescent composition.
本発明に係る発光組成物の製造方法によれば、蛍光体の表面の少なくとも一部に、物理気相成長法によって、少なくとも窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を形成する第１保護膜形成工程を有することから、耐湿性に優れた発光組成物を製造することが可能となる。 According to the method for producing a luminescent composition of the present invention, the first protective film containing at least nitrogen (N) or fluorine (F) is formed on at least a part of the surface of the phosphor by physical vapor deposition. Since it has a 1st protective film formation process, it becomes possible to manufacture the luminescent composition excellent in moisture resistance.
以下、図面を参照して本発明の実施の形態を説明する。
本実施形態においては、発光組成物が、表示装置（例えば液晶ディスプレイ）の光源装置（例えばバックライト装置）を構成する場合を例として説明を行う。
Embodiments of the present invention will be described below with reference to the drawings.
In the present embodiment, a case where the light emitting composition constitutes a light source device (for example, a backlight device) of a display device (for example, a liquid crystal display) will be described as an example.
図１に、本実施形態に係る光源装置を有する表示装置の概略構成図を示す。
この、本実施形態に係る表示装置１は、光源装置２及び光学装置３を有する。
FIG. 1 shows a schematic configuration diagram of a display device having a light source device according to the present embodiment.
The display device 1 according to this embodiment includes a light source device 2 and an optical device 3.
本実施形態において、光源装置２は、液晶装置を有する光学装置３に対する、バックライト装置である。
この光源装置２の、樹脂による導光部７内には、例えば青色ＬＥＤによる青色光源の表面に、多数の蛍光体を含む樹脂が塗布されて構成される、発光体６が設けられている。
また、本実施形態において、光源装置２の、光学装置３に対向する最近接部には、拡散シート９が設けられている。この拡散シート９は、青色光源や各蛍光体からの光を、光学装置３側へ面状に均一に導くものである。光源装置２の裏面側には、リフレクタ４が設けられている。また、必要に応じて、リフレクタ４と同様のリフレクタ５が、導光部７の側面にも設けられる。
なお、本実施形態に係る光源装置２において、導光部７を構成する樹脂は、エポキシ、シリコーン、ウレタンのほか、様々な透明樹脂を用いることができる。また、発光体６を構成する青色光源の形状も、サイドエミッタータイプや砲弾タイプなど、様々な種類のものから適宜選択して用いることができる。
In the present embodiment, the light source device 2 is a backlight device for the optical device 3 having a liquid crystal device.
In the light guide unit 7 made of resin of the light source device 2, for example, a light emitting body 6 configured by applying a resin containing a large number of phosphors on the surface of a blue light source of a blue LED is provided.
In the present embodiment, a diffusion sheet 9 is provided at the closest portion of the light source device 2 facing the optical device 3. The diffusion sheet 9 uniformly guides light from the blue light source and each phosphor to the optical device 3 side in a planar shape. A reflector 4 is provided on the back surface side of the light source device 2. Further, if necessary, a reflector 5 similar to the reflector 4 is also provided on the side surface of the light guide unit 7.
In the light source device 2 according to the present embodiment, the resin constituting the light guide unit 7 can use various transparent resins in addition to epoxy, silicone, and urethane. Further, the shape of the blue light source constituting the light emitter 6 can be appropriately selected from various types such as a side emitter type and a shell type.
一方、本実施形態において、光学装置３は、光源装置２からの光に対して変調を施すことにより所定の出力光を出力する液晶装置である。
この光学装置３においては、光源装置２に近い側から、偏向板１０と、ＴＦＴ（Thin Film Transistor；薄膜トランジスタ）用のガラス基板１１及びその表面のドット状電極１２と、液晶層１３及びその表裏に被着された配向膜１４と、電極１５と、電極１５上の複数のブラックマトリクス１６と、このブラックマトリクス１６間に設けられる画素に対応した第１（赤色）カラーフィルタ１７ａ，第２（緑色）カラーフィルタ１７ｂ，第３カラーフィルタ１７ｃと、ブラックマトリクス１６及びカラーフィルタ１７ａ〜１７ｃとは離れて設けられるガラス基板１８と、偏向板１９とが、この順に配置されている。
ここで、偏向板１０及び１９は、特定の方向に振動する光を形成するものである。また、ＴＦＴガラス基板１１とドット電極１２及び電極１５は、特定の方向に振動している光のみを透過する液晶層１３をスイッチングするために設けられるものであり、配向膜１４が併せて設けられることにより、液晶層１３内の液晶分子の傾きが一定の方向に揃えられる。また、ブラックマトリクス１６が設けられていることにより、各色に対応するカラーフィルタ１７ａ〜１７ｃから出力される光のコントラストの向上が図られている。これらのブラックマトリクス１６及びカラーフィルタ１７ａ及び１７ｃは、ガラス基板１８に取着される。
On the other hand, in this embodiment, the optical device 3 is a liquid crystal device that outputs predetermined output light by modulating light from the light source device 2.
In this optical device 3, from the side close to the light source device 2, the deflection plate 10, the glass substrate 11 for TFT (Thin Film Transistor) and the dot electrode 12 on the surface thereof, the liquid crystal layer 13 and the front and back thereof. The deposited alignment film 14, the electrode 15, a plurality of black matrices 16 on the electrode 15, and first (red) color filters 17 a and second (green) corresponding to the pixels provided between the black matrices 16. A glass substrate 18 and a deflecting plate 19 which are provided apart from the color filter 17b, the third color filter 17c, the black matrix 16 and the color filters 17a to 17c are arranged in this order.
Here, the deflecting plates 10 and 19 form light that vibrates in a specific direction. The TFT glass substrate 11, the dot electrode 12, and the electrode 15 are provided for switching the liquid crystal layer 13 that transmits only light oscillating in a specific direction, and the alignment film 14 is also provided. Thus, the inclination of the liquid crystal molecules in the liquid crystal layer 13 is aligned in a certain direction. Further, since the black matrix 16 is provided, the contrast of light output from the color filters 17a to 17c corresponding to the respective colors is improved. The black matrix 16 and the color filters 17 a and 17 c are attached to the glass substrate 18.
そして、本実施形態に係る光源装置２を構成する発光体６においては、各蛍光体の表面が、保護層によって覆われている。
なお、本実施形態において、青色光によって励起されて緑色光を発光する第１蛍光体（青緑色蛍光体または緑色蛍光体）の表面に第１保護膜が設けられた発光組成物を、本発明に係る発光組成物の第１の例である第１発光組成物とする。なお、青色光によって励起される第１蛍光体の例としては、ＳｒＧａ２Ｓ４：Ｅｕなどが挙げられる。
また、青色光によって励起されて赤色光を発光する第２蛍光体（黄色蛍光体や赤色蛍光体）の表面に第１保護膜が設けられた発光組成物を、本発明に係る発光組成物の第２の例である第２発光組成物とする。なお、青色光によって励起される第２蛍光体の例としては、アルカリ土類金属硫化物にＥｕ２＋を固溶させた蛍光体として、ＣａＳ：Ｅｕ、及びＳｒＳ：Ｅｕなどが挙げられる。
And in the light-emitting body 6 which comprises the light source device 2 which concerns on this embodiment, the surface of each fluorescent substance is covered with the protective layer.
In the present embodiment, a luminescent composition in which a first protective film is provided on the surface of a first phosphor (blue-green phosphor or green phosphor) that emits green light when excited by blue light is used in the present invention. It is set as the 1st light emitting composition which is the 1st example of the light emitting composition which concerns on this. Note that examples of the first phosphor excited by blue light include SrGa 2 S 4 : Eu.
Further, a luminescent composition in which a first protective film is provided on the surface of a second phosphor (yellow phosphor or red phosphor) that emits red light when excited by blue light is used as the luminescent composition according to the present invention. The second light-emitting composition as the second example is used. Examples of the second phosphor excited by blue light include CaS: Eu and SrS: Eu as phosphors obtained by dissolving Eu 2+ in alkaline earth metal sulfide.
図２Ａに、本実施形態に係る発光組成物の、一部を拡大した断面図を示す。
本実施形態に係る発光組成物２１は、蛍光体２２の表面の少なくとも一部が、例えばスパッタ等の物理気相成長（Physical Vapor Deposition；ＰＶＤ）法によって、保護層に覆われて構成されている。本実施形態において、保護層は、窒素（Ｎ）またはフッ素（Ｆ）を含む、第１保護膜２３を有している。
このように、少なくとも窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜２３で覆われることにより、蛍光体２２と空気中の水分との接触面積を十分に低減させることができる。したがって、この構成によれば、蛍光体２２の耐湿性向上が図られる。すなわち、発光組成物２１は、本来耐湿性が充分でない蛍光体２２を含みながらも、優れた長期信頼性を示す。
なお、第１保護膜２３が、蛍光体２２の露出領域２２ａをとり囲むように、つまり蛍光体２２の露出領域２２ａが非連続となるように設けられている場合には、特に耐湿性の向上が図られると考えられる。
FIG. 2A shows a partially enlarged cross-sectional view of the luminescent composition according to this embodiment.
The luminescent composition 21 according to the present embodiment is configured such that at least a part of the surface of the phosphor 22 is covered with a protective layer by, for example, a physical vapor deposition (PVD) method such as sputtering. . In the present embodiment, the protective layer has a first protective film 23 containing nitrogen (N) or fluorine (F).
Thus, by covering with the first protective film 23 containing at least nitrogen (N) or fluorine (F), the contact area between the phosphor 22 and moisture in the air can be sufficiently reduced. Therefore, according to this configuration, the moisture resistance of the phosphor 22 can be improved. That is, the light-emitting composition 21 exhibits excellent long-term reliability while including the phosphor 22 that originally has insufficient moisture resistance.
In addition, when the 1st protective film 23 is provided so that the exposure area | region 22a of the fluorescent substance 22 may be surrounded, ie, the exposure area | region 22a of the fluorescent substance 22 may be discontinuous, improvement of moisture resistance especially. It is thought that is planned.
また、本実施形態に係る発光組成物２１は、蛍光体表面を第１保護膜２３が覆うのみならず、例えば図２Ｂに示すように、この第１保護膜２３とは異なる材料組成の第２保護膜２４が蛍光体表面に設けられた構成（積層構造）としても良い。この第２保護膜２４の材料組成としては、例えばケイ素（Ｓｉ）や酸素（Ｏ）によるガラスなどが挙げられる。
このような積層構造による保護層は、蛍光体２２の表面が粗雑であるなど、スパッタによる第１保護膜のみでは耐湿性が充分向上するほど表面を覆えない場合や、蛍光体の特性（耐湿性または発光特性）と使用条件との関係から更に耐湿性を向上させる必要があると考えられる場合には、特に有効と考えられる。
In addition, the luminescent composition 21 according to the present embodiment not only covers the phosphor surface with the first protective film 23 but also a second material composition different from that of the first protective film 23 as shown in FIG. 2B, for example. It is good also as a structure (laminated structure) in which the protective film 24 was provided in the fluorescent substance surface. Examples of the material composition of the second protective film 24 include glass made of silicon (Si) or oxygen (O).
In such a protective layer having a laminated structure, the surface of the phosphor 22 is rough. For example, the first protective film formed by sputtering alone cannot cover the surface enough to improve the moisture resistance, or the characteristics of the phosphor (moisture resistance). Or, when it is considered necessary to further improve the moisture resistance from the relationship between the light emission characteristics) and the use conditions, it is considered to be particularly effective.
この、第１保護膜２３と第２保護膜２４とを有する保護層においては、ガラスのように液相法で形成される第２保護膜２４が、蛍光体２２の表面のうち、物理気相成長法によって形成される第１保護膜２３が付着しにくい箇所にも付着する。すなわち、第１保護膜２３と第２保護膜２４とは、蛍光体２２の表面において付着しやすい位置が互いに異なる。このような相補的な被覆によって、第１保護膜２３と第２保護膜２４とを有する保護層においては、第１保護膜２３や第２保護膜２４の一方のみを有する保護層に比べて、蛍光体２２に対する保護層の被覆率（保護性能）の向上が図られる。
なお、図２Ｃに示すように、蛍光体２２と第１保護膜２３との間に、第２保護膜２４が挟み込まれるような形で発光組成物２１が構成されることが好ましい。このような発光組成物２１は、その作製において、第１保護膜２３の形成よりも先に、液相法による第２保護膜２４の形成が行われるため、液相法の過程で第１保護膜２３が溶出することを回避できるためである。
In the protective layer having the first protective film 23 and the second protective film 24, the second protective film 24 formed by a liquid phase method such as glass is a physical vapor phase in the surface of the phosphor 22. The first protective film 23 formed by the growth method also adheres to a place where it is difficult to adhere. That is, the first protective film 23 and the second protective film 24 are different from each other in the position where they easily adhere to the surface of the phosphor 22. By such a complementary coating, in the protective layer having the first protective film 23 and the second protective film 24, compared to the protective layer having only one of the first protective film 23 and the second protective film 24, The coverage (protective performance) of the protective layer with respect to the phosphor 22 is improved.
As shown in FIG. 2C, it is preferable that the luminescent composition 21 is configured such that the second protective film 24 is sandwiched between the phosphor 22 and the first protective film 23. In the production of such a light emitting composition 21, the second protective film 24 is formed by the liquid phase method prior to the formation of the first protective film 23. This is because the film 23 can be prevented from eluting.
このような、本実施形態に係る発光組成物によれば、蛍光体の耐湿性向上を図ることができる。
また、このような、本実施形態に係る発光組成物を有する光源装置や表示装置においては、発光組成物の耐湿性向上によって、表示装置の長期信頼性の向上が図られる。
According to such a light emitting composition according to this embodiment, it is possible to improve the moisture resistance of the phosphor.
Moreover, in such a light source device and display device having the light emitting composition according to this embodiment, the long-term reliability of the display device is improved by improving the moisture resistance of the light emitting composition.
＜実施例＞
本発明の実施例について説明する。
<Example>
Examples of the present invention will be described.
まず、本実施例に係る発光組成物の製造方法について説明する。本実施例に係る発光組成物の製造は、図３に示す製造装置（スパッタ装置）３１を用いて行った。
スパッタターゲット３２としては、Si3N4を用いた。
作製手順として、まず、粒径が１〜５０μｍ程度の蛍光体（本実施例ではアルカリ土類金属硫化物、CaS:Eu）３３を２ｇ採取し、スパッタ装置内に設置したφ６０ｍｍのカップ３４に入れる。カップ３４とターゲット３２の距離を約５ｃｍ程度とした。
続いて、製造装置３１内の圧力を、０．４×１０−４Ｐａ以下まで下げて脱気したのち、不活性ガスを導入した。本実施例では、不活性ガスの組成をＡｒ／Ｎ２＝１／２とした。続いて、装置内の圧力を０．８Ｐａ程度に調整し、プラズマを発生させ、スパッタを開始した。ここで、アルゴンと窒素の比率としてはＡｒ／Ｎ２＝１／１〜１／４程度までが適しており、スパッタ時の圧力は０．１〜１０Ｐａ程度が適しているが、必要な膜質とスパッタ速度を勘案して調整した。
なお、スパッタを行っている間、モータ３５によってカップ３４を振動させ、粉体状の蛍光体３３を流動，回転させることにより、全ての蛍光体に対して全面的に均一なコーティング（保護膜の形成）がなされるよう配慮した。振動条件は、カップ３４のサイズや粉体（蛍光体３３）の量などを適宜調整することで最適化を図った。本実施例では、１０〜６０Ｈｚの間で、適宜変動させて行った。
コーティングの量をスパッタ時間によって調整しながら、このようにして第１保護膜形成工程を行い、蛍光体表面の少なくとも一部が窒化シリコン（ＳｉＮ）を主成分とする第１保護膜による保護層で覆われる発光組成物を得た。
First, the manufacturing method of the luminescent composition which concerns on a present Example is demonstrated. The light emitting composition according to this example was manufactured using a manufacturing apparatus (sputtering apparatus) 31 shown in FIG.
As the sputter target 32, Si 3 N 4 was used.
As a manufacturing procedure, first, 2 g of a phosphor (alkaline earth metal sulfide, CaS: Eu) 33 having a particle diameter of about 1 to 50 μm is sampled and placed in a φ34 mm cup 34 installed in the sputtering apparatus. . The distance between the cup 34 and the target 32 was about 5 cm.
Then, after reducing the pressure in the manufacturing apparatus 31 to 0.4 × 10 −4 Pa or less and degassing, an inert gas was introduced. In this example, the composition of the inert gas was Ar / N 2 = 1/2. Subsequently, the pressure in the apparatus was adjusted to about 0.8 Pa, plasma was generated, and sputtering was started. Here, the ratio of argon to nitrogen is suitably about Ar / N 2 = 1/1 to 1/4, and the pressure during sputtering is suitably about 0.1 to 10 Pa. Adjustment was made in consideration of the sputtering rate.
During the sputtering, the cup 34 is vibrated by the motor 35 and the powdery phosphor 33 is flowed and rotated, so that a uniform coating (protective film of the protective film) is applied to all phosphors. The formation was considered. The vibration conditions were optimized by appropriately adjusting the size of the cup 34 and the amount of the powder (phosphor 33). In the present embodiment, the measurement was performed by appropriately varying between 10 and 60 Hz.
The first protective film forming step is performed in this manner while adjusting the amount of coating by the sputtering time, and at least a part of the phosphor surface is a protective layer made of the first protective film mainly composed of silicon nitride (SiN). A covered luminescent composition was obtained.
次に、このような条件で作製した発光組成物に対する、紫外線照射に対する電子発生量の測定結果について説明する。測定は、スパッタによるコーティング量を変化させて複数種類の発光組成物を作製し、これらの発光組成物への紫外線照射に対する電子放出性を、仕事関数測定装置（理研計器製ＡＣ−１）を用いて行った。なお、第１保護膜なしのサンプル（従来の蛍光体）についても、同様に測定を行った。
測定結果を、図４に示す。図４において、横軸は照射される紫外線のエネルギー、縦軸は１秒間あたりの電子発生数を示す。また、図４に示す測定結果のうち、曲線ａは第１保護膜のない従来の蛍光体、曲線ｂは蛍光体に対する重量比で１％だけ第１保護膜が形成された発光組成物、曲線ｃは蛍光体に対する重量比で３％だけ第１保護膜が形成された発光組成物、曲線ｄは蛍光体に対する重量比で１０％の第１保護膜が形成された発光組成物についての測定結果を示す。
なお、紫外線照射に対する電子の発生量は、非金属である蛍光体（アルカリ土類金属硫化物など）においては、イオン化傾向を反映していると考えられる。例えば、コーティング量が増加するほど電子の発生量が低下している傾向が確認できたが、水分によって蛍光体が変質する際にはイオン化の過程を経ると考えられるため、湿度に対する耐久性が向上すると推定される。
Next, the measurement result of the electron generation amount with respect to ultraviolet irradiation with respect to the luminescent composition produced on such conditions is demonstrated. The measurement is performed by changing the coating amount by sputtering to produce a plurality of types of luminescent compositions, and using a work function measuring apparatus (AC-1 manufactured by Riken Keiki Co., Ltd.) to measure the electron emission properties of these luminescent compositions against ultraviolet irradiation. I went. Note that the same measurement was performed on a sample without the first protective film (conventional phosphor).
The measurement results are shown in FIG. In FIG. 4, the horizontal axis represents the energy of the irradiated ultraviolet light, and the vertical axis represents the number of electrons generated per second. Also, among the measurement results shown in FIG. 4, curve a is a conventional phosphor without the first protective film, curve b is a luminescent composition in which the first protective film is formed by 1% by weight ratio to the phosphor, and curve c is a light-emitting composition in which the first protective film is formed by 3% by weight with respect to the phosphor, and curve d is a measurement result with respect to the light-emitting composition in which the first protective film is formed by 10% by weight with respect to the phosphor. Indicates.
In addition, it is thought that the generation amount of the electron with respect to ultraviolet irradiation reflects the ionization tendency in phosphors (such as alkaline earth metal sulfides) that are non-metals. For example, it was confirmed that the amount of generated electrons decreased as the coating amount increased. However, when the phosphor is altered by moisture, it is considered that the phosphor undergoes an ionization process, thus improving durability against humidity. It is estimated that.
図４に示す測定結果において、まず、曲線ａ〜ｄのピークの高さについては、従来の蛍光体に比べて、３％の第１保護膜を有する発光組成物が１０分の１以下、１０％の第１保護膜を有する発光組成物が２０分の１以下となっている。
また、図４の測定結果において、曲線のピークの高さは、主に保護層の厚さに依存すると考えられる。したがって、本実施例における測定結果からは、蛍光体に対して少なくとも３％の重量を有する第１保護膜が形成されていれば、蛍光体が全面的に（完全ではなくともほぼ全体が）第１保護膜によって覆われ、充分な耐湿性向上が図られると考えられる。
なお、このピークは、前述した仕事関数測定装置の機器性能（６ｅＶ以上では紫外線の強度が低くなる）によって生じている。したがって、異なる測定装置を用いて測定を行う際には、ピークが生じない場合もあり得る。
In the measurement results shown in FIG. 4, first, regarding the heights of the peaks of the curves a to d, the light emitting composition having 3% of the first protective film is less than one-tenth compared with the conventional phosphor. % Of the light emitting composition having the first protective film of 1/20 or less.
In the measurement result of FIG. 4, the height of the peak of the curve is considered to depend mainly on the thickness of the protective layer. Therefore, from the measurement results in this example, if the first protective film having a weight of at least 3% with respect to the phosphor is formed, the phosphor is entirely (although not completely) first. 1 It is considered that the film is covered with a protective film to sufficiently improve the moisture resistance.
This peak is caused by the device performance of the above-described work function measuring apparatus (the intensity of ultraviolet light is reduced at 6 eV or more). Therefore, when a measurement is performed using a different measuring apparatus, a peak may not occur.
また、図４に示す測定結果において、曲線ａ〜ｄの立ち上がりの位置（電子放出が観測され始める位置）は、３％以上の第１保護膜を有する発光組成物において略一定（６．０ｅＶ近傍）となっている。
この測定結果における曲線の立ち上がりの位置は、主に蛍光体表面の性質に依存すると考えられる。したがって、やはり本実施例における測定結果からは、蛍光体に対して少なくとも３％の重量を有する第１保護膜が形成されていれば、蛍光体が全面的に（完全ではなくともほぼ全体が）第１保護膜によって覆われ、充分な耐湿性向上が図られると考えられる。
In the measurement results shown in FIG. 4, the rising positions of the curves a to d (positions at which electron emission starts to be observed) are substantially constant (near 6.0 eV) in the light emitting composition having the first protective film of 3% or more. ).
The rising position of the curve in this measurement result is considered to depend mainly on the properties of the phosphor surface. Therefore, from the measurement results in this example, if the first protective film having a weight of at least 3% with respect to the phosphor is formed, the phosphor is entirely (although not completely). It is considered that the film is covered with the first protective film and the moisture resistance is sufficiently improved.
なお、図４の測定結果は、蛍光体としてアルカリ土類金属硫化物（CaS:Eu）を含む発光組成物に関するものである。蛍光体の種類が異なれば、曲線の立ち上がりの位置なども変化するが、あくまで図４の測定結果から相対的に変化するにとどまると考えられる。すなわち、蛍光体の種類が異なっても、図４に示した測定結果に基づいて第１保護膜の量と耐湿性との関係を推定することが可能であると考えられる。 Note that the measurement results in FIG. 4 relate to a luminescent composition containing alkaline earth metal sulfide (CaS: Eu) as a phosphor. If the type of the phosphor is different, the position of the rising edge of the curve also changes, but it is considered that it changes only relative to the measurement result of FIG. That is, it is considered that the relationship between the amount of the first protective film and the moisture resistance can be estimated based on the measurement result shown in FIG.
次に、蛍光体に対する第１保護膜の形成（コーティング）によって得られた発光組成物のＴＥＭ写真を図５Ａに示す。この発光組成物は、第１保護膜を重量比で１０％コーティングしたもの（図４における曲線ｄに対応）である。図中ｘで示した灰色の部分が、第１保護膜（コーティング保護層）である。図５ＡのＴＥＭ写真から、蛍光体の表面が、第１保護膜によって連続的にコーティングされていることが確認できた。すなわち、蛍光体の露出する露出領域は、この連続的な第１保護膜によって、点在する程度の非連続なものにされていると考えられる。
また、この部分をＥＤＸ（エネルギー分散型Ｘ線スペクトロスコピー）により組成分析した。結果を図５Ｂに示す。この組成分析結果から、第１保護膜にＳｉ及びＮが含まれていることが明らかとなった。したがって第１保護膜は、窒素含有ケイ素化合物の膜であると考えられる。
Next, FIG. 5A shows a TEM photograph of the luminescent composition obtained by forming (coating) the first protective film on the phosphor. This luminescent composition is a first protective film coated with 10% by weight (corresponding to curve d in FIG. 4). The gray portion indicated by x in the figure is the first protective film (coating protective layer). From the TEM photograph of FIG. 5A, it was confirmed that the surface of the phosphor was continuously coated with the first protective film. That is, it is considered that the exposed region where the phosphor is exposed is made discontinuous to the extent that it is scattered by the continuous first protective film.
Further, this portion was subjected to composition analysis by EDX (energy dispersive X-ray spectroscopy). The result is shown in FIG. 5B. From the result of the composition analysis, it became clear that the first protective film contains Si and N. Therefore, the first protective film is considered to be a film of a nitrogen-containing silicon compound.
次に、本実施例に係る発光組成物の、２５℃，７５％ＲＨの条件下における信頼性試験の結果を、図６に示す。この試験は、第１保護膜を蛍光体に対して重量比で１０％コーティングした発光組成物（図４における曲線ｄに対応）について行った。なお、第１保護膜なしのサンプル（従来の蛍光体）についても、同様に試験を行った。
図６の結果より、未処理サンプル（従来の蛍光体；図中ｙ）に比べて、本実施例に係る発光組成物（図中ｚ）は、耐久性が向上していることが明らかとなった
また、この本実施例に係る発光組成物を用いてＬＥＤ（図１における発光体６）を作製し、４５℃、９０％ＲＨでの耐久試験を行ったところ、輝度の低下はみられなかった。なお、従来のＬＥＤでは、同様の条件で耐久試験を行ったところ、２４０時間で焼く２６％の輝度低下が認められた。
Next, FIG. 6 shows the result of the reliability test of the luminescent composition according to this example under the conditions of 25 ° C. and 75% RH. This test was performed on a luminescent composition (corresponding to curve d in FIG. 4) in which the first protective film was coated on the phosphor by 10% by weight. Note that the same test was performed on a sample without the first protective film (conventional phosphor).
From the results of FIG. 6, it is clear that the durability of the luminescent composition according to this example (z in the figure) is improved as compared with the untreated sample (conventional phosphor; y in the figure). Further, when an LED (light emitting body 6 in FIG. 1) was produced using the light emitting composition according to this example and subjected to a durability test at 45 ° C. and 90% RH, no decrease in luminance was observed. It was. The conventional LED was subjected to a durability test under the same conditions. As a result, a 26% reduction in luminance was observed in 240 hours.
なお、保護層（本実施例では第１保護膜）の厚さについて、前述した電子の放出性の変化やＴＥＭ観察と、輝度の低下率などとを考え併せて検討を行った結果、本実施例に係る発光組成物では、５ｎｍ以上の厚さが最適と考えられた。
保護層の厚さの選定は、蛍光体の平均粒子径（または比表面積）に基づいて行った。
具体的には、蛍光体が球形であると仮定し、蛍光体の比重をρ1、平均粒子径をｒ、採取重量をＷ1とした。また、第１保護膜の材料（スパッタターゲットの材料）の比重をρ2、コーティングする（つまり最終的に形成される第１保護膜の）重量をＷ2とし、かつ、Ｗ２をスパッタレート（ｃｍ／ｈ）とスパッタ時間（ｈ）、カップ３４内の被スパッタ領域の開口面積（ｃｍ２）及びρ2の積として求めた。このとき、重量比率（Ｗ2／（Ｗ1＋Ｗ２））をｘとすると、第１保護膜の厚さｄ（ｃｍ）は〔数１〕で表される。
The thickness of the protective layer (the first protective film in this embodiment) was examined in consideration of the above-described change in electron emission, TEM observation, luminance reduction rate, and the like. In the luminescent composition according to the example, a thickness of 5 nm or more was considered optimal.
The thickness of the protective layer was selected based on the average particle diameter (or specific surface area) of the phosphor.
Specifically, assuming that the phosphor is spherical, the specific gravity of the phosphor is ρ 1 , the average particle diameter is r, and the collected weight is W 1 . Further, the specific gravity of the material of the first protective film (sputter target material) is ρ 2 , the weight of the coating (that is, the first protective film finally formed) is W 2 , and W 2 is the sputter rate ( cm / h), sputtering time (h), opening area (cm 2 ) of the sputtered region in the cup 34, and ρ 2 . At this time, when the weight ratio (W 2 / (W 1 + W 2 )) is x, the thickness d (cm) of the first protective film is expressed by [Equation 1].
［数１］
ｄ＝ｒ・（3√（1+ｘ・ρ1／（1−ｘ）・ρ2）−１）
[Equation 1]
d = r · ( 3 √ (1 + x · ρ 1 / (1−x) · ρ 2 ) −1)
ここで、ｒ＞＞ｄの場合は、蛍光体の比表面積をｓ1（ｃｍ2／ｇ）とすると、第１保護膜の厚さｄ（ｃｍ）は、〔数２〕で近似的に表せる。 Here, in the case of r >> d, when the specific surface area of the phosphor is s 1 (cm 2 / g), the thickness d (cm) of the first protective film can be approximately expressed by [Equation 2]. .
［数２］
ｄ＝Ｗ2／（ｓ1×Ｗ１×ρ2）
[Equation 2]
d = W 2 / (s 1 × W 1 × ρ 2 )
したがって、蛍光体の平均粒子径(比表面積)を把握できれば、これに基づいて、採取する蛍光体の量やスパッタ時間、及び被スパッタ領域の開口面積（例えば使用する容器の開口部面積）などとの関係から、第１保護膜の厚さを調整することができ、最適な厚さを求めることも可能となる。
なお、保護層（本実施例では第１保護膜）の厚さの上限は、蛍光体粒子の径の半分と考えられる。これより大きいと、輝度などの発光特性が著しく損なわれるおそれが生じるためである。
Therefore, if the average particle diameter (specific surface area) of the phosphor can be grasped, based on this, the amount of phosphor to be collected, the sputtering time, the opening area of the sputtered region (for example, the opening area of the container to be used), etc. Therefore, the thickness of the first protective film can be adjusted, and the optimum thickness can be obtained.
Note that the upper limit of the thickness of the protective layer (first protective film in this embodiment) is considered to be half the diameter of the phosphor particles. This is because if it is larger than this, the light emission characteristics such as luminance may be significantly impaired.
以上の実施の形態及び実施例で説明したように、本実施形態に係る発光組成物によれば、耐湿性の向上が図られる。
また、本実施形態に係る光源装置によれば、発光組成物の耐湿性向上によって、光源装置の長期信頼性の向上が図られる。すなわち、この光源装置を有する、本実施形態に係る表示装置によれば、表示装置の長期信頼性の向上が図られる。
また、本実施形態（実施例）に係る発光組成物の製造方法によれば、耐湿性に優れた発光組成物を製造することが可能となる。
As described in the above embodiments and examples, according to the luminescent composition according to this embodiment, the moisture resistance is improved.
Moreover, according to the light source device which concerns on this embodiment, the improvement of long-term reliability of a light source device is achieved by the improvement in the moisture resistance of a luminescent composition. That is, according to the display device according to this embodiment having this light source device, the long-term reliability of the display device can be improved.
Moreover, according to the manufacturing method of the luminescent composition which concerns on this embodiment (Example), it becomes possible to manufacture the luminescent composition excellent in moisture resistance.
また、本実施形態に係る光源装置及び表示装置によれば、従来の、青，緑，赤の各色すべてをＬＥＤ等の直接駆動型光源によって得る構成に比べて簡潔な駆動回路によりながらも、長期信頼性の向上が図られる。
また、本実施形態に係る光源装置及び表示装置によれば、近紫外域の光を蛍光体の励起光源とする構成に比べた場合、耐湿性の向上のみならず、周辺部材（樹脂やＬＥＤチップ等）の劣化と併せて、長期信頼性を特に向上させることができる。
In addition, according to the light source device and the display device according to the present embodiment, although a simple drive circuit is used as compared with the conventional configuration in which all the colors of blue, green, and red are obtained by a direct drive type light source such as an LED, it is long-term. Reliability is improved.
In addition, according to the light source device and the display device according to the present embodiment, when compared with a configuration in which light in the near ultraviolet region is used as a phosphor excitation light source, not only the moisture resistance is improved, but also the peripheral member (resin or LED chip). Etc.) and long-term reliability can be particularly improved.
なお、以上の実施の形態の説明で挙げた使用材料及びその量、処理時間及び寸法などの数値的条件は好適例に過ぎず、説明に用いた各図における寸法形状及び配置関係も概略的なものである。すなわち、本発明は、この実施の形態に限られるものではない。 Note that the numerical conditions such as the materials used, the amount thereof, the processing time, and the dimensions mentioned in the description of the above embodiments are only suitable examples, and the dimensions, shapes, and arrangement relationships in the drawings used for the description are also schematic. Is. That is, the present invention is not limited to this embodiment.
例えば、蛍光体の種類については、CaS:Euに限られず、サヨガレート系や硫化カルシウム系などのアルカリ土類金属硫化物をはじめ、様々な蛍光体を用いることができる。
また、例えば、第１保護膜の材料組成についても、窒素またはフッ素を含んでいれば、他の材料と組み合わせて構成されていても良い。ここで、他の材料としては、チタン酸化物，ビスマス酸化物，ニオブ酸化物，スズ酸化物，インジウム酸化物，ケイ素酸化物，及びランタンやニオブをドープしたSrTiO3のような、酸化物などが挙げられる。
For example, the type of phosphor is not limited to CaS: Eu, and various phosphors such as alkaline earth metal sulfides such as sayogalate and calcium sulfide can be used.
In addition, for example, the material composition of the first protective film may be configured in combination with other materials as long as it contains nitrogen or fluorine. Here, other materials include titanium oxide, bismuth oxide, niobium oxide, tin oxide, indium oxide, silicon oxide, and oxides such as SrTiO 3 doped with lanthanum or niobium. Can be mentioned.
また、例えば、前述の実施例ではスパッタターゲットとしてSi3N4を用いる例を説明したが、スパッタターゲットとしてSiを用い、実際にスパッタを行う際にN2ガスを供給しても良い。 Further, for example, in the above-described embodiment, an example in which Si 3 N 4 is used as a sputtering target has been described. However, Si may be used as a sputtering target, and N 2 gas may be supplied when actual sputtering is performed.
また、例えば、図２Ｂや図２Ｃに示した、第１保護膜及び第２保護膜の積層による保護層については、その形成にあたり、液相による第２保護膜のコーティング（第２保護膜形成工程）と、気相による第１保護膜のコーティング（第１保護膜形成工程）とを繰り返して行うことによって、ガラスと窒素含有ケイ素化合物との繰り返し積層構造を得て、更に耐湿性に優れた発光組成物を構成することもできるなど、本発明は、種々の変形及び変更をなされ得る。 Further, for example, the protective layer formed by stacking the first protective film and the second protective film shown in FIGS. 2B and 2C is coated with the second protective film by a liquid phase (second protective film forming step). ) And coating of the first protective film by the gas phase (first protective film forming step) is repeated to obtain a repetitive laminated structure of glass and a nitrogen-containing silicon compound, and further, light emission excellent in moisture resistance The present invention can be modified and changed in various ways, such as a composition.
１・・・表示装置、２・・・光源装置、３・・・光学装置、４・・・リフレクタ、５・・・リフレクタ、６・・・発光体、７・・・導光部、９・・・拡散シート、１０・・・偏向板、１１・・・ＴＦＴガラス基板、１２・・・ドット電極、１３・・・液晶層、１４・・・配向膜、１５・・・電極、１６・・・ブラックマトリクス、１７ａ・・・第１カラーフィルタ、１７ｂ・・・第２カラーフィルタ、１７ｃ・・・第３カラーフィルタ、１８・・・ガラス基板、１９・・・偏向板、２１・・・発光組成物、２２・・・蛍光体、２２ａ，２２ｂ・・・露出領域、２３・・・第１保護膜、２４・・・第２保護膜、３１・・・製造装置、３２・・・スパッタターゲット、３３・・・蛍光体、３４・・・カップ、３５・・・モータ DESCRIPTION OF SYMBOLS 1 ... Display apparatus, 2 ... Light source device, 3 ... Optical apparatus, 4 ... Reflector, 5 ... Reflector, 6 ... Light-emitting body, 7 ... Light guide part, 9 * .. Diffusion sheet, 10 ... deflecting plate, 11 ... TFT glass substrate, 12 ... dot electrode, 13 ... liquid crystal layer, 14 ... alignment film, 15 ... electrode, 16 ... Black matrix, 17a ... first color filter, 17b ... second color filter, 17c ... third color filter, 18 ... glass substrate, 19 ... deflecting plate, 21 ... light emission Composition: 22 ... phosphor, 22a, 22b ... exposed region, 23 ... first protective film, 24 ... second protective film, 31 ... production apparatus, 32 ... sputter target 33 ... phosphor 34 ... cup 35 ... motor
Claims (14)
上記蛍光体の表面の少なくとも一部が、保護層によって覆われ、
上記保護層が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有する
ことを特徴とする発光組成物。 A luminescent composition comprising a phosphor,
At least a part of the surface of the phosphor is covered with a protective layer,
The said protective layer has a 1st protective film containing nitrogen (N) or fluorine (F). The luminescent composition characterized by the above-mentioned.
ことを特徴とする請求項１に記載の発光組成物。 The luminescent composition according to claim 1, wherein the protective layer has a second protective film in contact with the first protective film and having a material composition different from that of the first protective film.
ことを特徴とする請求項１に記載の発光組成物。 The average thickness of the said protective layer is 5 nm or more and below the radius of the said fluorescent substance. The luminescent composition of Claim 1 characterized by the above-mentioned.
ことを特徴とする請求項１に記載の発光組成物。 The luminescent composition according to claim 1, wherein the first protective film contains silicon (Si).
ことを特徴とする請求項１に記載の発光組成物。 The luminescent composition according to claim 1, wherein an exposed region where the phosphor is exposed is discontinuous by the first protective film.
ことを特徴とする請求項１に記載の発光組成物。 The luminescent composition according to claim 1, wherein the phosphor is excited by blue light.
上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、上記青色光源からの青色光によって励起される蛍光体を含み、
上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、蛍光体の表面の少なくとも一部が、保護層によって覆われ、上記保護層が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有する
ことを特徴とする光源装置。 A light source device having a first light emitting composition, a second light emitting composition, and a blue light source,
At least one of the first light emitting composition and the second light emitting composition includes a phosphor excited by blue light from the blue light source,
At least one of the first light emitting composition and the second light emitting composition is such that at least a part of the surface of the phosphor is covered with a protective layer, and the protective layer is formed of nitrogen (N) or fluorine (F). A light source device comprising: a first protective film including:
ことを特徴とする請求項７に記載の光源装置。 The light source device according to claim 7, wherein both the first light emitting composition and the second light emitting composition include a phosphor excited by blue light from the blue light source.
この光源装置からの光に対して所定の変調を施し、所定の出力光を出力する光学装置と、
を有する表示装置であって、
上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、上記青色光源からの青色光によって励起される蛍光体を含み、
上記第１発光組成物及び上記第２発光組成物のうち、少なくとも一方は、蛍光体の表面の少なくとも一部が、保護層によって覆われ、上記保護層が、窒素（Ｎ）またはフッ素（Ｆ）を含む第１保護膜を有する
ことを特徴とする表示装置。 A light source device having a first light emitting composition, a second light emitting composition, and a blue light source;
An optical device that performs predetermined modulation on the light from the light source device and outputs predetermined output light;
A display device comprising:
At least one of the first light emitting composition and the second light emitting composition includes a phosphor excited by blue light from the blue light source,
At least one of the first light emitting composition and the second light emitting composition is such that at least a part of the surface of the phosphor is covered with a protective layer, and the protective layer is formed of nitrogen (N) or fluorine (F). A display device comprising: a first protective film including:
ことを特徴とする請求項９に記載の表示装置。 The display device according to claim 9, wherein both the first light emitting composition and the second light emitting composition include a phosphor excited by blue light from the blue light source.
ことを特徴とする発光組成物の製造方法。 And a first protective film forming step of forming a first protective film containing at least nitrogen (N) or fluorine (F) by physical vapor deposition on at least a part of a surface of the phosphor. A method for producing the composition.
ことを特徴とする請求項１１に記載の発光組成物の製造方法。 The method for producing a luminescent composition according to claim 11, wherein the phosphor is a phosphor excited by blue light.
ことを特徴とする請求項１１に記載の発光組成物の製造方法。 The method for producing a luminescent composition according to claim 11, wherein the physical vapor deposition method is performed while contacting the phosphor with nitrogen gas (N 2 ).
ことを特徴とする請求項１１に記載の発光組成物の製造方法。 The light emitting device according to claim 11, further comprising a second protective film forming step of forming a second protective film having a material composition different from that of the first protective film separately from the first protective film forming step. A method for producing the composition.
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