JPH0249090A - Fluorescent substance consisting of bn(c,h) - Google Patents
Fluorescent substance consisting of bn(c,h)Info
- Publication number
- JPH0249090A JPH0249090A JP20099688A JP20099688A JPH0249090A JP H0249090 A JPH0249090 A JP H0249090A JP 20099688 A JP20099688 A JP 20099688A JP 20099688 A JP20099688 A JP 20099688A JP H0249090 A JPH0249090 A JP H0249090A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- phosphor
- carbon
- film
- light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000126 substance Substances 0.000 title abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 23
- 230000005284 excitation Effects 0.000 claims description 14
- 239000007789 gas Substances 0.000 abstract description 19
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000012159 carrier gas Substances 0.000 abstract description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RBWMYPKAPIYTJQ-VMBFOHBNSA-N (1R,2S,5S)-6,6-dimethyl-N-[(2S)-1-oxo-3-[(3S)-2-oxopyrrolidin-3-yl]propan-2-yl]-3-[2-[4-(trifluoromethoxy)phenoxy]acetyl]-3-azabicyclo[3.1.0]hexane-2-carboxamide Chemical compound CC1([C@@H]2[C@H]1[C@H](N(C2)C(=O)COC3=CC=C(C=C3)OC(F)(F)F)C(=O)N[C@@H](C[C@@H]4CCNC4=O)C=O)C RBWMYPKAPIYTJQ-VMBFOHBNSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 229910015844 BCl3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はホウ素、炭素、窒素および水素からなる螢光体
、特に高温においても使用でき、高効率でかつ減衰の速
い螢光体に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a phosphor made of boron, carbon, nitrogen and hydrogen, and particularly to a phosphor that can be used even at high temperatures, has high efficiency, and has fast decay. be.
［従来技術］
光を吸収して可視部付近の別の波長の光を発する螢光体
は古くから知られており、用途に応じて種々の螢光体が
使用されている。螢光体には硫化物や酸化物等の各種母
体結晶に付活剤を添加したものと、遷移金属イオンを含
んだ絶縁体やアントラセン、ターフェニル等の共役した
π電子を有する有機化合物のような物質自体で螢光を発
するもの等がある。しかしこれらはいずれも螢光体それ
自体が耐熱性に乏しいか、あるいは高温では螢光を発し
ないものがほとんどであり、高温で使用できる螢光体と
して優れたものがないのが現状である。一方、耐熱性に
優れた材料である窒化ホウ素−（ｈ−ＢＮ）に物理的に
カーボンをドープしたものが螢光を発し、高温でも発光
することが報告［江良皓：窒化はう素に関する研究 第
７章、無機材質研究所研究報告書２７号（１９８１）］
されている、このものはカーボン発熱体の炉内でｈ−Ｂ
Ｎを焼成して得るものであるが、炭素のｈ−ＢＮ結晶格
子間への混入の程度をコントロールすることが困難であ
る。また、ｈ−ＢＮとカーボンを混合して焼成して炭素
量を制御したものを得ることも可能であるが、この場合
にはトータル炭素の制御は可能であるものの、ｈ−ＢＮ
結晶格子間に混入した炭素の量の制御はできないもので
あり、螢光体としての物性を自由にコントロールするこ
とは困難である。また、フリーの炭素の存在は光を吸収
するため螢光体としての光利用効率が低下する等の問題
点がある。[Prior Art] Fluorescent materials that absorb light and emit light of different wavelengths near the visible region have been known for a long time, and various fluorescent materials are used depending on the purpose. Fluorescent materials include those made by adding activators to various host crystals such as sulfides and oxides, as well as insulators containing transition metal ions and organic compounds with conjugated π electrons such as anthracene and terphenyl. There are some substances that emit fluorescence by themselves. However, most of these phosphors either have poor heat resistance or do not emit fluorescence at high temperatures, and currently there is no excellent phosphor that can be used at high temperatures. On the other hand, it has been reported that boron nitride (h-BN), a material with excellent heat resistance, physically doped with carbon emits fluorescence and emits light even at high temperatures [Hiro Era: Research on boron nitride Chapter 7, Inorganic Materials Research Institute Research Report No. 27 (1981)]
This one is h-B in the furnace of carbon heating element.
Although it is obtained by firing N, it is difficult to control the degree of carbon incorporation into the h-BN crystal lattice. It is also possible to mix and sinter h-BN and carbon to obtain a product with a controlled amount of carbon, but in this case, although it is possible to control the total carbon, h-BN
It is not possible to control the amount of carbon intermixed between the crystal lattices, and it is difficult to freely control the physical properties of the phosphor. Furthermore, the presence of free carbon causes problems such as a decrease in light utilization efficiency as a phosphor because it absorbs light.
Ｅ問題点を解決するための具体的手段］本発明者らはか
かる問題点に鑑み鋭意検討の結果、三塩化ホウ素、アン
モニア、アセチレン等のガスを用いて化学気相析出法（
以下ＣＶＤ法という）によりホウ素、炭素、窒素および
水素からなる均一な物質［以下ＢＮ （Ｃ，Ｈ）と記す
］が特異な螢光特性を有することを見いだし本発明に到
達したものである。すなわち本発明は２７０ ｎｍの励
起光により３４０ｎｍ、３５５ｎｍの位置に、また３１
３ｎｍの励起光により４０８ｎｍ、４３３ｎｍの位置に
それぞれ螢光ピークを有することを特徴とするＢＮ （
Ｃ，Ｈ）からなる螢光体である。Specific Means for Solving Problem E] In view of these problems, the present inventors have conducted intensive studies and have developed a chemical vapor deposition method (
The present invention was achieved by discovering that a homogeneous substance consisting of boron, carbon, nitrogen, and hydrogen (hereinafter referred to as BN (C, H)) has unique fluorescent properties using the CVD method (hereinafter referred to as CVD method). That is, in the present invention, excitation light of 270 nm can be used to generate light at 340 nm, 355 nm, and 31 nm.
BN (
C, H).
本発明の螢光体は励起光が興なる（主として２７０ｎｍ
、３１３ｎｍの２点）発光群が存在するものである。こ
の理由はＢＮ （Ｃ，Ｈ）の電子構造にいくつかの不純
物準位が存在するためと考えられる。The phosphor of the present invention emits excitation light (mainly 270 nm).
, 313 nm 2 points) Emission group exists. The reason for this is thought to be that several impurity levels exist in the electronic structure of BN (C, H).
本発明の螢光体と組成的には類似の螢光体であるｈ−Ｂ
Ｎに物理的にカーボンをドープしたもの（先に示した江
良晧：窒化はう素に関する研究）は３００ｎｍの励起光
による３２０．３３７．３５５．３７２ｎｍに螢光ピー
クを有し、本発明の螢光体とは異なった螢光特性であり
、両者は明確に区別できるものである。h-B, a phosphor compositionally similar to the phosphor of the present invention;
The material in which N is physically doped with carbon (research on boron nitride by Akira Era mentioned earlier) has a fluorescence peak at 320.337.355.372 nm when excited by 300 nm, and the fluorescence of the present invention It has different fluorescent characteristics from that of a photon, and the two can be clearly distinguished.
本発明の螢光体は励起光と放射光の波長差が大であり、
可視光領域にも螢光が得られるため幅広い用途に使用で
きるとともに効率のよい螢光体となるものである。さら
に本発明の螢光体はそれ自体耐熱性に優れるものである
が、高温（７００℃近辺）においても優れた螢光特性を
有している。The phosphor of the present invention has a large wavelength difference between excitation light and emission light,
Since it can produce fluorescence even in the visible light range, it can be used in a wide range of applications and is an efficient phosphor. Furthermore, the phosphor of the present invention itself has excellent heat resistance, and has excellent fluorescent properties even at high temperatures (around 700° C.).
螢光とはその発光時間が約０．１秒までのものを言い、
これ以上発光が持続するものをリン光と言うが、本発明
の螢光体は螢光のほかリン光も発するものである０例え
ば、Ｃｉ ０．６％、Ｈ： １．５％を含むＢＮ （Ｃ
，Ｈ）は２６０〜３１０ ｎ ｍ （特に２７０ ｎｍ
）の励起光で３８０〜４２０ ｎ ｍ （特に３９５〜
４００ｎｍ）のリン光（この波長のリン光は青紫）を減
衰時間２４秒で発する。また、２７０〜３４０ｎｍ（特
に３１３ｎｍ）の励起光で５００〜５５０（特に５１０
〜５３０ｎｍ）のリン光（この波長のリン光は緑〜黄緑
）を減衰時間２４秒で発するものであり、これら全体と
してのリン光は緑色である。Fluorescence refers to something whose luminescence time is up to about 0.1 seconds.
Anything that continues to emit light longer than this is called phosphorescence, and the phosphor of the present invention emits phosphorescence as well as fluorescence.For example, BN containing 0.6% Ci and 1.5% H. (C
, H) is 260 to 310 nm (especially 270 nm
) with excitation light of 380-420 nm (especially 395-420 nm)
400 nm) (phosphorescence at this wavelength is blue-violet) with a decay time of 24 seconds. In addition, 500 to 550 (especially 510 nm) excitation light of 270 to 340 nm (especially 313 nm)
~530 nm) (phosphorescence of this wavelength is green to yellow-green) with a decay time of 24 seconds, and the phosphorescence as a whole is green.
本発明の螢光体は、本質的にホウ素、炭素、窒素および
水素からなり、ＣｕＫα線によるＸ線回折測定による２
θが２０〜３０＠の範囲に回折ピークを有することを特
徴とする。また、その製造法は、ホウ素源ガス、炭素源
ガス、窒素源ガスおよびキャリヤーガスからなる混合ガ
スをＣＶＤ法により反応させる方法である。The phosphor of the present invention essentially consists of boron, carbon, nitrogen and hydrogen, and has a
It is characterized by having a diffraction peak in the range of θ of 20 to 30@. Moreover, the manufacturing method is a method in which a mixed gas consisting of a boron source gas, a carbon source gas, a nitrogen source gas, and a carrier gas is reacted by a CVD method.
この方法による場合ホウ素、窒素の比は原子比でほぼ１
：１であり、残部が炭素と水素である。In this method, the ratio of boron and nitrogen is approximately 1 in terms of atomic ratio.
:1, with the remainder being carbon and hydrogen.
水素は原料の組成に関係なく０〜３重量％の範囲となる
。炭素は原料ガスの炭素量に依存し、広い範囲にわたり
存在し得るが、本発明が目的とする螢光体としては、０
．０１〜５重量％、より好ましくは０．３〜ｌｌｉ量％
の範囲である。炭素がこれ以下では螢光を全く発しない
か、または極めて弱く、これより多い場合にも螢光が非
常に弱（なる。Hydrogen is in the range of 0 to 3% by weight regardless of the composition of the raw material. Carbon depends on the amount of carbon in the raw material gas and can exist over a wide range, but as a phosphor for the purpose of the present invention, carbon can be present in a wide range.
．． 01-5% by weight, more preferably 0.3-lli%
is within the range of If the amount of carbon is less than this, the fluorescence will not emit at all or it will be very weak, and if it is more than this, the fluorescence will be very weak.
本発明の螢光体を製造するためのＣＶＤ法ガス原料とし
ては、特に限定されないが、ホウ素源としては、ＢＣｌ
３等のハロゲン化ホウ素、窒素源としてはＮＨ３等の反
応性の高いガスが好ましく、炭素源としては、炭化水素
、特に不飽和結合を有するガスが好ましく、反応性等か
らアセチレンが最も好ましい、また、均質な螢光体を再
現性よく得るためには、これら原料ガスに加えてキャリ
ヤーガスの使用が好ましく、水素ガス、アルゴン等を用
いることができる。The CVD method gas raw material for producing the phosphor of the present invention is not particularly limited, but the boron source is BCl
As the nitrogen source, a highly reactive gas such as NH3 is preferable, and as the carbon source, a hydrocarbon, especially a gas having an unsaturated bond, is preferable, and acetylene is most preferable from the viewpoint of reactivity. In order to obtain a homogeneous phosphor with good reproducibility, it is preferable to use a carrier gas in addition to these raw material gases, and hydrogen gas, argon, etc. can be used.
これら原料ガスの量的関係については特に制限されない
が、ホウ素源ガスと窒素源ガスは少なくとも原子比で、
１：２以上が好ましい、これ以下ではホウ素源ガスとし
てＢＣｌ３を用いた場合、生成物中にＣＩが残る等の不
都合がある。There is no particular restriction on the quantitative relationship between these raw material gases, but the boron source gas and nitrogen source gas have at least an atomic ratio of
A ratio of 1:2 or more is preferred; if it is less than this, when BCl3 is used as the boron source gas, there are disadvantages such as CI remaining in the product.
このようにして得られる螢光体は、反応条件により基板
に被着した形の膜、これが厚み方向に成長した塊状体、
あるいは粉体等積々の形態があるが、これらいずれの形
態においても螢光特性を有するものである。The phosphor obtained in this way consists of a film adhered to the substrate depending on the reaction conditions, a lump formed by growing the film in the thickness direction,
Alternatively, it may be in the form of a pile, such as a powder, but any of these forms has fluorescent properties.
反応温度は特に限定的ではないが、６００ ”Ｃ以上が
好ましい、これ以下では反応速度が極端に小さくなる１
反応速度の面からは反応温度は高い方が好ましいが、当
然基体の耐熱温度に依存する。Although the reaction temperature is not particularly limited, it is preferably 600"C or higher; below this temperature, the reaction rate becomes extremely low.
From the viewpoint of reaction rate, a higher reaction temperature is preferable, but it naturally depends on the heat resistance temperature of the substrate.
また、反応温度が高いほど生成物の水素量は少なくなる
。Furthermore, the higher the reaction temperature, the lower the amount of hydrogen in the product.
本発明のＢＮ （Ｃ，Ｈ）が螢光を発する理由は必ずし
も定かではないが、５．２ｅＶの広いバンドギャップを
有するｈ−ＢＮの格子点がＣあるいはＨにより置換され
、不純物準位を形成し、その準位間の遷移が光の吸収、
発光を生じるためと推定される。The reason why the BN (C, H) of the present invention emits fluorescence is not necessarily clear, but the lattice points of h-BN, which has a wide band gap of 5.2 eV, are substituted with C or H, forming an impurity level. The transition between the levels causes light absorption,
It is presumed that this is because it generates light emission.
本発明の螢光体は種々の用途に供することができ、例え
ば放射線シンチレータ、高速応答ブラウン管等が挙げら
れる。The phosphor of the present invention can be used in various applications, such as radiation scintillators, high-speed response cathode ray tubes, and the like.
以下、実施例により本発明をより具体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
内径４０露園長さ１０００ｍ鳳の石英管からなる熱ＣＶ
Ｄ１ｉｔの中央に５００ｍ５＋ Ｘ ２０ｍｍＸ ３
ａｍのニッケル基板を設置し、ＢＣ１３、Ｃ２Ｈｚおよ
びＮ Ｈ３を原料とし、Ｈ２をキャリヤーガスとして、
反応管中央を８００℃に加熱した炉内に導入した。それ
ぞれのガス流量は次のとおりである。Example 1 Thermal CV consisting of a quartz tube with an inner diameter of 40 mm and a length of 1000 m
500m5+ x 20mm x 3 in the center of D1it
A nickel substrate of am is installed, BC13, C2Hz and NH3 are used as raw materials, H2 is used as a carrier gas,
The center of the reaction tube was introduced into a furnace heated to 800°C. The respective gas flow rates are as follows.
Ｂ ＣＩ ３ １５ｃｃ／ｗｉｎ Ｎ Ｈ３３０ｃｃ／５ｉｎ Ｃ２Ｈ２８ｃｃ／ −１ｎ Ｈ２１４４ｃｃ／ ｓｉｎ 炉内圧力は大気圧でおこなった。B CI 3 15cc/win N H330cc/5in C2H28cc/-1n H2144cc/sin The pressure inside the furnace was atmospheric pressure.
以上の条件で６時間反応をおこなったのち、ガス導入と
基板加熱をやめ、炉内を真空排気、冷却した。基板上に
は、全幅（２０ｍｍ）にわたり、ガス導入側より約５０
ｍｍ、の範囲で膜が形成された。After the reaction was carried out for 6 hours under the above conditions, gas introduction and substrate heating were stopped, and the inside of the furnace was evacuated and cooled. Approximately 50 mm is placed on the substrate from the gas introduction side over the entire width (20 mm).
A film was formed in the range of mm.
冷却により基板上の膜は簡単に剥離し、得られた膜は茶
色半透明であり、厚さ約１２０．ｃｒｍの膜であり、自
由に取り扱える程度の強度を有していた。Upon cooling, the film on the substrate was easily peeled off, and the resulting film was brown and translucent, and had a thickness of approximately 120 mm. It was a crm film and had enough strength to be handled freely.
このＷＡ（生成膜）を窒素ガス中１６００℃で１時間熱
処理して白色不透明の膜（焼成膜）とした、このものの
元素分析をおこなったところ炭素０．６重量％、水素１
．５ ｊＩ量％であった。This WA (produced film) was heat-treated for 1 hour at 1600°C in nitrogen gas to form a white opaque film (fired film). Elemental analysis of this film revealed that carbon was 0.6% by weight and hydrogen was 1% by weight.
．． It was 5 jI amount%.
生成膜と焼成膜とをＣｕＫα線によるＸ線回折測定をお
こない、この回折パターンを第１図（生成膜）、第２図
（焼成膜）に示した。第１図において、２θが２０〜３
０℃においてブロードなピークを有し、無定形ＢＮと無
定形Ｃの００２の回折ピークが重なりあったものである
。この生成膜は、結晶化度が低く、ブロードなパターン
となることが特徴であり、窒化ホウ素、炭素の粉末由来
のものと明確に区別できる。生成膜を焼成して得た膜は
第２図に示したとおり、２θが２６°においてＢＮとＣ
の００２の回折ピークが重なりあったピークとなるが、
これはｈ−Ｂ Ｎ、 ｈ−Ｃの００２の回折ピーク（２
θが２６．５＠’）よりも低角度であることが特徴であ
り、焼成によっても回折ピークが顕著には鋭くならない
ものである。The produced film and the fired film were subjected to X-ray diffraction measurements using CuKα rays, and the diffraction patterns are shown in FIG. 1 (produced film) and FIG. 2 (fired film). In Figure 1, 2θ is 20 to 3
It has a broad peak at 0°C, and the 002 diffraction peaks of amorphous BN and amorphous C overlap. This produced film is characterized by a low crystallinity and a broad pattern, and can be clearly distinguished from those derived from boron nitride and carbon powders. As shown in Figure 2, the film obtained by firing the produced film has BN and C at 2θ of 26°.
The diffraction peaks of 002 and 002 are overlapping peaks, but
This is the 002 diffraction peak (2
It is characterized in that the angle θ is lower than 26.5@'), and the diffraction peak does not sharpen significantly even after firing.
焼成膜を■日立製作新製６５０−１０型分光螢光光度計
によりその螢光スペクトルを測定し、第３図および第４
図に示した＊ ３４０ ｎ ｍおよび３５５ｎｍの螢光
（放射光）は２７０ｎｍの励起光により効率よく励起さ
れ、非常に鋭いピークを示した（第３図）、一方、４０
８ｎｍおよび４３３ｎｍの螢光は３１３ｎｍの励起光に
よって効率よく励起された（第、４図）、各々の代表的
な放射光を一定にして励起光を操作させたときのスペク
トルを第５図（（＆）、（ｂ））に示した。The fluorescence spectrum of the fired film was measured using a new model 650-10 spectrofluorophotometer manufactured by Hitachi.
*The fluorescent light (emission light) at 340 nm and 355 nm shown in the figure was efficiently excited by the 270 nm excitation light and showed a very sharp peak (Figure 3);
Fluorescence at 8 nm and 433 nm was efficiently excited by excitation light at 313 nm (Figure 4). Figure 5 shows the spectrum when the excitation light was manipulated while keeping the typical emitted light constant. &), (b)).
また、同一装置により励起光を３００ｎｍとする以外は
同一条件で測定した焼成前の化１１ｉ膜の螢光スペクト
ルを第６図に示した。この膜は茶色半透明であり、３５
０ｎｍに螢光を発したが、焼成膜に比べてブロードであ
り、また励起光も明確に決めることができない、この膜
のＸ＠回折図（第１図参照）にはブロードな回折線が観
察され、結晶状態がアモルファスに近いことがわかる。Further, FIG. 6 shows the fluorescence spectrum of the compound 11i film before firing, which was measured using the same apparatus under the same conditions except that the excitation light was 300 nm. This film is brown and translucent, and 35
Fluorescence was emitted at 0 nm, but it was broader than that of the fired film, and the excitation light could not be determined clearly. Broad diffraction lines were observed in the X@ diffraction diagram of this film (see Figure 1). It can be seen that the crystalline state is close to amorphous.
螢光のピークがブロードであるのはこの結晶状態の低さ
に起因するものと考えられる。The reason why the fluorescence peak is broad is considered to be due to this low crystalline state.
実施例２〜７
実施例１と同じ装置を用いてガス組成、反応条件を種々
変えて反応をおこない、生成物はすべて窒素気流中１６
００℃で１時間熱処理をおこなった。Examples 2 to 7 Reactions were carried out using the same equipment as in Example 1 with various gas compositions and reaction conditions, and all products were produced in a nitrogen stream at 16
Heat treatment was performed at 00°C for 1 hour.
反応条件および焼成物の組成、螢光特性を実施例１の結
果とともに第１表に示した。The reaction conditions, composition of the fired product, and fluorescent properties are shown in Table 1 along with the results of Example 1.
比較例１
市販のＢＮ粉（電気化学工業■製）を黒鉛加熱炉に入れ
窒素気流中２０００°Ｃで熱処理をおこなった。Comparative Example 1 Commercially available BN powder (manufactured by Denki Kagaku Kogyo ■) was placed in a graphite heating furnace and heat-treated at 2000°C in a nitrogen stream.
この粉の炭素および水素含有量は０．７重量％および０
．８重量％であった。この粉の螢光スペクトル（励起光
を３００ｎｍとする以外は実施例１と同一の条件で測定
）を第７図に示す、ここに観察された全螢光（３２０，
３３７，３５５，３７２）はすべて３００ｎｍの光によ
って効率よく励起された（第８図（ａｌ）、なお、参考
のため４１２ｎｍの弱い放射光に対する励起スペクトル
を測定したところ３６３ｎｍにピークを有していた（第
８図山））、これらの螢光特性は実施例１〜７のＣＶＤ
法によるＢＮ （Ｃ，Ｈ）と全く異なっている。The carbon and hydrogen content of this powder is 0.7% by weight and 0.
．． It was 8% by weight. The fluorescence spectrum of this powder (measured under the same conditions as Example 1 except that the excitation light was 300 nm) is shown in Figure 7, and the total fluorescence observed here (320 nm,
337, 355, 372) were all efficiently excited by 300 nm light (Figure 8 (al); for reference, the excitation spectrum for weak 412 nm radiation was measured and found to have a peak at 363 nm. (Fig. 8 mountain)), these fluorescent properties were determined by the CVD of Examples 1 to 7.
This is completely different from BN (C, H) according to the law.
［発明の効果］
本発明の螢光体は、耐熱性、化学的安定性、耐熱衝撃性
等に優れた螢光体であり、高温においても良好な螢光特
性を有するとともに励起光と放射光の波長差が大であり
、可視光領域にも螢光が得られ、幅広い用途に適用でき
る効率のよい螢光体である。また、本発明の螢光体はＣ
ＶＤ法により容易にかつ再現性よく得られるものである
。[Effects of the Invention] The phosphor of the present invention is a phosphor with excellent heat resistance, chemical stability, thermal shock resistance, etc., and has good fluorescent properties even at high temperatures and is compatible with excitation light and emitted light. It has a large wavelength difference and can emit fluorescence even in the visible light range, making it an efficient phosphor that can be used in a wide range of applications. Further, the phosphor of the present invention is C
It can be obtained easily and with good reproducibility by the VD method.
第１図は実施例１の生成膜のＸ線回折パターン、第２図
は実施例１の焼成膜のＸ線回折パターンを示す、第３図
および第４図は実施例１の焼成膜の螢光スペクトル、第
５図（（ａｔ、（ｂ））は実施例１の焼成膜の励起スペ
クトルを示す、第６図は実施例１の生成膜の螢光スペク
トルを示す、第７図は比較例１の螢光スペクトルを示す
、第８図（（ｈ）、伽））は比較例１の励起スペクトル
を示す。
第５図
（α）
Ｒ’Ｈ光； ３４Ｃｈｔｍ
（ｂ、）
放飼光； ４０８７１罹
波
長／ｘｍ
放射％；３２０請
）皮
長
ｌＴＬ机
図
（ｂ）
波
長
／
孔′ｍ、FIG. 1 shows the X-ray diffraction pattern of the produced film of Example 1, FIG. 2 shows the X-ray diffraction pattern of the fired film of Example 1, and FIGS. 3 and 4 show the X-ray diffraction pattern of the fired film of Example 1. Optical spectra, FIG. 5 ((at, (b)) shows the excitation spectrum of the fired film of Example 1, FIG. 6 shows the fluorescence spectrum of the produced film of Example 1, and FIG. 7 shows the comparative example. FIG. 8 ((h), 弽)), which shows the fluorescence spectrum of Comparative Example 1, shows the excitation spectrum of Comparative Example 1. Figure 5 (α) R'H light; 34Chtm (b,) Release light; 40871 affected wavelength/xm Radiation %;
Claims (1)
位置に、また３１３ｎｍの励起光により４０８ｎｍ、４
３３ｎｍの位置にそれぞれ螢光ピークを有することを特
徴とするＢＮ（Ｃ，Ｈ）からなる螢光体。270 nm excitation light at 340 nm and 355 nm positions, and 313 nm excitation light at 408 nm and 4
A phosphor made of BN (C, H), characterized in that each has a fluorescence peak at a position of 33 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20099688A JPH0249090A (en) | 1988-08-11 | 1988-08-11 | Fluorescent substance consisting of bn(c,h) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20099688A JPH0249090A (en) | 1988-08-11 | 1988-08-11 | Fluorescent substance consisting of bn(c,h) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0249090A true JPH0249090A (en) | 1990-02-19 |
Family
ID=16433773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20099688A Pending JPH0249090A (en) | 1988-08-11 | 1988-08-11 | Fluorescent substance consisting of bn(c,h) |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0249090A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0411688A (en) * | 1990-04-27 | 1992-01-16 | Natl Inst For Res In Inorg Mater | Bn(c, h) phosphor for corpuscular ray |
| JP2005097022A (en) * | 2003-09-22 | 2005-04-14 | Japan Science & Technology Agency | Synthetic method for group iiib nitride |
| WO2006001194A1 (en) * | 2004-06-24 | 2006-01-05 | Sumitomo Electric Industries, Ltd. | Fluorescent substance and process for producing the same, and particle dispersion-type el device using the same |
| JP2006312672A (en) * | 2005-05-09 | 2006-11-16 | National Institute For Materials Science | Boron nitride crystal having fluorescence emission properties added with activator such as rare earth element, its manufacturing method and boron nitride phosphor |
| JP2018087278A (en) * | 2016-11-28 | 2018-06-07 | 国立研究開発法人物質・材料研究機構 | Phosphor, method for producing the same, luminescent device thereof, and ultraviolet use device thereof |
| JP2018086108A (en) * | 2016-11-28 | 2018-06-07 | 国立研究開発法人物質・材料研究機構 | Phototherapy device |
-
1988
- 1988-08-11 JP JP20099688A patent/JPH0249090A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0411688A (en) * | 1990-04-27 | 1992-01-16 | Natl Inst For Res In Inorg Mater | Bn(c, h) phosphor for corpuscular ray |
| JP2005097022A (en) * | 2003-09-22 | 2005-04-14 | Japan Science & Technology Agency | Synthetic method for group iiib nitride |
| WO2006001194A1 (en) * | 2004-06-24 | 2006-01-05 | Sumitomo Electric Industries, Ltd. | Fluorescent substance and process for producing the same, and particle dispersion-type el device using the same |
| JP2006312672A (en) * | 2005-05-09 | 2006-11-16 | National Institute For Materials Science | Boron nitride crystal having fluorescence emission properties added with activator such as rare earth element, its manufacturing method and boron nitride phosphor |
| JP2018087278A (en) * | 2016-11-28 | 2018-06-07 | 国立研究開発法人物質・材料研究機構 | Phosphor, method for producing the same, luminescent device thereof, and ultraviolet use device thereof |
| JP2018086108A (en) * | 2016-11-28 | 2018-06-07 | 国立研究開発法人物質・材料研究機構 | Phototherapy device |
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