JPH0260706B2 - - Google Patents
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- Publication number
- JPH0260706B2 JPH0260706B2 JP8926286A JP8926286A JPH0260706B2 JP H0260706 B2 JPH0260706 B2 JP H0260706B2 JP 8926286 A JP8926286 A JP 8926286A JP 8926286 A JP8926286 A JP 8926286A JP H0260706 B2 JPH0260706 B2 JP H0260706B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- zno
- mol
- brightness
- mixed
- 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.)
- Expired
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 74
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 61
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 41
- 238000010304 firing Methods 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- -1 lithium halide Chemical class 0.000 claims description 15
- 238000010894 electron beam technology Methods 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 40
- 239000011787 zinc oxide Substances 0.000 description 36
- 239000011701 zinc Substances 0.000 description 13
- 230000004907 flux Effects 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- MBHNWCYEGXQEIT-UHFFFAOYSA-N Fluphenazine hydrochloride Chemical compound Cl.Cl.C1CN(CCO)CCN1CCCN1C2=CC(C(F)(F)F)=CC=C2SC2=CC=CC=C21 MBHNWCYEGXQEIT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- MNKMDLVKGZBOEW-UHFFFAOYSA-M lithium;3,4,5-trihydroxybenzoate Chemical compound [Li+].OC1=CC(C([O-])=O)=CC(O)=C1O MNKMDLVKGZBOEW-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、例えば、100V以下の低い加速電圧
による電子の射突により青色に発光する低速電子
線用蛍光体に係わり、特に硫黄（Ｓ）成分が含有
してなく蛍光表示管用に適する酸化物系の低速電
子用蛍光体及びその製造方法に関するものであ
る。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a phosphor for slow electron beams that emits blue light due to the bombardment of electrons with a low accelerating voltage of, for example, 100 V or less. The present invention relates to an oxide-based phosphor for low-speed electrons that does not contain components and is suitable for use in fluorescent display tubes, and a method for producing the same.
従来、低速電子線用蛍光体で青色に発光する蛍
光体としては、ZnS：〔Zn〕やZnS：Ag＋In2O3
等の硫化物系の蛍光体が一般に知られており、蛍
光表示管に青色発光蛍光体として多く使用されて
いる。
Conventionally, phosphors for slow electron beams that emit blue light include ZnS: [Zn] and ZnS:Ag+In 2 O 3
Sulfide-based phosphors are generally known, and are often used as blue-emitting phosphors in fluorescent display tubes.
蛍光表示管は、第１図及び第２図に示すよう
に、絶縁性を有する基板１に配線導体２を被着
し、さらにこの配線導体２上の所定位置にスルー
ホール３ａの形成された絶縁層３を印刷し積層さ
せる。 As shown in FIGS. 1 and 2, a fluorescent display tube includes a wiring conductor 2 attached to an insulating substrate 1, and an insulating layer with through holes 3a formed at predetermined positions on the wiring conductor 2. Print and laminate layer 3.
前記スルーホール３ａ上に陽極導体４を印刷形
成させる。陽極導体４は、スルーホール３ａ中に
も充填され、配線導体２と接触し電気的に導通し
ている。この陽極導体４上に低速電子線用蛍光体
を被着して蛍光体層５を形成する。 An anode conductor 4 is printed on the through hole 3a. The anode conductor 4 is also filled in the through hole 3a and is in contact with the wiring conductor 2 to be electrically conductive. A phosphor for low-speed electron beams is deposited on the anode conductor 4 to form a phosphor layer 5.
前記陽極導体４と蛍光体層５により陽極６が構
成される。陽極６に対面する上方にはメツシユ状
の制御電極７が配設されている。さらに制御電極
７の上方にはフイラメント状の陰極８が張設され
ている。この陰極８は、タングステンの芯線とそ
の表面に被着されたアルカリ土類金属からなる酸
化物層（Ca、Sr、Ba）から構成されている。 The anode conductor 4 and the phosphor layer 5 constitute an anode 6. A mesh-shaped control electrode 7 is disposed above facing the anode 6. Further, a filament-shaped cathode 8 is stretched above the control electrode 7 . This cathode 8 is composed of a tungsten core wire and an oxide layer (Ca, Sr, Ba) made of an alkaline earth metal deposited on its surface.
前記陽極、制御電極、陰極等の電極を、基板１
とこの基板１の周縁から立設した側面板９と、前
記基板１に対面する前面板１０により構成された
外囲器で覆い、外囲器内を真空に保持している。 The electrodes such as the anode, control electrode, and cathode are connected to the substrate 1.
The substrate 1 is covered with an envelope composed of a side plate 9 standing upright from the periphery of the substrate 1 and a front plate 10 facing the substrate 1, and the inside of the envelope is kept in a vacuum.
このように構成された蛍光表示管に、前記
ZnS：〔Zn〕やZnS：Ag＋In2O3等の硫化物系蛍
光体を被着して発光させるには、陰極８から放出
された電子が制御電極７により加速制御されて陽
極導体が印加された陽極６の蛍光体層５に射突す
ることによつて発光する。 The above-mentioned method is applied to the thus configured fluorescent display tube.
To emit light by depositing a sulfide-based phosphor such as ZnS: [Zn] or ZnS:Ag+In 2 O 3 , electrons emitted from the cathode 8 are accelerated and controlled by the control electrode 7 and applied to the anode conductor. When the light impinges on the phosphor layer 5 of the anode 6, light is emitted.
しかし、電子が蛍光体層５に射突する際に硫化
物系蛍光体の一部が分解して、Ｓ、SO、SO2等
の硫化物系のガスが飛散する。この硫化物系のガ
スがフイラメント状陰極８に付着すると、その表
面に被着された酸化物層と反応し、陰極８の表面
を毒化して、陰極のエミツシヨン特性を劣化さ
せ、陰極８の寿命を短くさせたり、蛍光表示管の
輝度を低くする等の問題点を有していた。 However, when electrons impinge on the phosphor layer 5, a portion of the sulfide-based phosphor is decomposed, and sulfide-based gases such as S, SO, and SO 2 are scattered. When this sulfide-based gas adheres to the filament cathode 8, it reacts with the oxide layer deposited on its surface, poisoning the surface of the cathode 8, deteriorating the emission characteristics of the cathode, and reducing the lifespan of the cathode 8. This had problems such as shortening the length of the display and lowering the brightness of the fluorescent display tube.
そこで硫化物系以外の青色発光蛍光体が要求さ
れるようになつた。そして、硫化物系以外の低速
電子線用蛍光体で青色発光をする蛍光体の一つに
Ａ（Zn1-X，Mgx）Ｏ・Ga2O3（但し、0.6≦Ａ≦
1.2及び０≦ｘ≦0.5である）の組成式で示される
ガリウム酸塩系複合酸化物蛍光体が特公昭60−
31236号で公知である。発光色はｘ＝０だと青色
であり、ｘを増たしていくと長波側にシフトして
緑色に近くなるが、発光しきい値電圧は高くな
る。 Therefore, a demand for blue-emitting phosphors other than sulfide-based phosphors has arisen. One of the non-sulfide-based phosphors for slow electron beams that emits blue light is A(Zn 1-X , Mgx)O.Ga 2 O 3 (where 0.6≦A≦
1.2 and 0≦x≦0.5).
It is known from No. 31236. The emission color is blue when x=0, and as x is increased, it shifts to the longer wavelength side and becomes closer to green, but the emission threshold voltage becomes higher.
このＡ（Zn1-X，Mgx）Ｏ・Ga2O3蛍光体は、
酸化亜鉛（ZnO）と酸化マグネシウム（MgO）
と酸化ガリウム（Ga2O3）をＡ及びｘの値になる
ような割分で混合し、この混合物を耐熱性容器に
詰めて、空気中、又は中性あるいは弱還元性雰囲
気中で1200〜1400℃の高温で２〜４時間焼成した
後粉砕混合操作を行い、更に同じ焼成条件で焼成
する。これを数回繰返し行うことにより前記組成
式で示される蛍光体が得られる。 This A(Zn 1-X , Mgx)O・Ga 2 O 3 phosphor is
Zinc oxide (ZnO) and magnesium oxide (MgO)
and gallium oxide (Ga 2 O 3 ) in proportions that match the values of A and x, this mixture is packed in a heat-resistant container, and heated to 1200 ~ After firing at a high temperature of 1400°C for 2 to 4 hours, a pulverization and mixing operation is performed, and further firing is performed under the same firing conditions. By repeating this several times, a phosphor having the above compositional formula can be obtained.
しかし、前記蛍光体に於いてＡ＝1x＝０であ
るZnO・Ga2O3蛍光体に於いて陽極電圧を80V、
陰極電圧0.6V印加しても、4ft―Ｌ程度と発光輝
度が低く、改善の余地があつた。また、Ａ＝１、
ｘ＝0.3になるようにMgOを混合した（Zn0.3，
Mg0.3）Ｏ・Ga2O3蛍光体にすると、発光波長が
長波側に移り輝度が多少上るが陽極電圧が80V、
陰極電圧が0.6V印加したときに8ft―Ｌであり、
実用上はまだ低くかつた。そして低電圧で駆動さ
せるためには、Ga2O31モルに対する（Zn1-x，
Mgx）０のモル数、すなわち前記組成式のＡの
値で変化し、Ａの値が0.9≦Ａ≦1.0の範囲の輝度
が高くなる範囲であると記載されているが、Ａが
1.0以上多くしたデータは記載されていない。い
ずれにしても従来のＡ（Zn1-x，Mgx）０・Ga2O3
蛍光体はさらに高輝度化及び低電圧化が要求され
ていた。 However, in the ZnO・Ga 2 O 3 phosphor where A=1x=0 in the phosphor, the anode voltage is 80V,
Even when a cathode voltage of 0.6V was applied, the luminance was low at about 4ft-L, and there was room for improvement. Also, A=1,
MgO was mixed so that x = 0.3 (Zn 0.3 ,
When using Mg 0.3 ) O・Ga 2 O 3 phosphor, the emission wavelength shifts to the longer wavelength side and the brightness increases somewhat, but the anode voltage is 80V,
When the cathode voltage is 0.6V applied, it is 8ft-L,
In practical terms, it was still too low. In order to drive at low voltage , (Zn 1-x ,
It is stated that the number of moles of Mgx) 0, that is, the value of A in the above composition formula changes, and that the brightness is high when the value of A is 0.9≦A≦1.0.
Data increased by 1.0 or more are not recorded. In any case, the conventional A(Zn 1-x , Mgx)0・Ga 2 O 3
Phosphors were required to have even higher brightness and lower voltage.
一方、一般式がM1-xO1-yXy、但し母体金属Ｍ
はZnもしくはZnおよびMgであり、ｘはハロゲン
元素、ｘ及びｙの範囲は0.0001≦ｘ≦0.005、
0.0001≦ｙ≦0.005である蛍光体で特公昭60−
7674号で公知である。この蛍光体は母体金属ZnO
又は（Zn，Mg）Ｏにハロゲン元素をドープする
ことにより低抵抗化させ、低速電子線で励起させ
て発光することが可能になる。このようにハロゲ
ン元素は低抵抗させるのに有効な元素であること
が公知である。 On the other hand, the general formula is M 1-x O 1-y X y , but the base metal M
is Zn or Zn and Mg, x is a halogen element, the range of x and y is 0.0001≦x≦0.005,
A phosphor with 0.0001≦y≦0.005, which
It is known from No. 7674. This phosphor is made of matrix metal ZnO
Alternatively, by doping (Zn, Mg)O with a halogen element, the resistance can be lowered and it can be excited with a slow electron beam to emit light. As described above, halogen elements are known to be effective elements for lowering resistance.
また、Li元素は、ガリウム酸塩とはなじみやす
く、高温でガリウム酸リチウムをつくり、この物
質は高電圧で発光する発光物質であることが特公
昭48−43030号で公知である。 Furthermore, it is known from Japanese Patent Publication No. 48-43030 that the Li element is compatible with gallates and forms lithium gallate at high temperatures, and this material is a luminescent material that emits light at high voltage.
さらに従来のZnO・Ga2O3蛍光体の製造方法は
焼成温度が1000℃以上と高く、耐熱容器の構成成
分や炉内の飛散物等を溶かし込み易く、純度の良
いものができずらいというばかりでなく、熱効率
も悪く、高温で結晶を急成長させるので結晶状態
も良くなかつた。 Furthermore, the conventional manufacturing method for ZnO/Ga 2 O 3 phosphors requires a high firing temperature of over 1,000°C, which makes it difficult to produce products with high purity because the components of the heat-resistant container and debris from the furnace are easily dissolved. Not only that, but the thermal efficiency was poor, and the crystal condition was not good because the crystals grew rapidly at high temperatures.
そこで本発明は、前述の公知の蛍光体等に着目
し、ZnO・Ga2O3にハロゲン元素及びLi元素をド
ープして低速電子線でも青色に発光することが可
能であり、発光輝度も一般使用に可能な程度に高
いZnO・Ga2O3系の蛍光体を提供することを第１
の目的とするものである。
Therefore, the present invention focused on the above-mentioned known phosphors and doped ZnO/Ga 2 O 3 with halogen elements and Li elements, which makes it possible to emit blue light even with low-speed electron beams, and the emission brightness is also lower than that of the ordinary one. The first objective is to provide a ZnO・Ga 2 O 3 -based phosphor that is as high as possible for use.
This is the purpose of
また、前記蛍光体を製造するのにハロゲン化リ
チウムを融剤として用いることにより焼成温度が
1000℃以下にして、結晶成長に適する新しい製造
方法を提供することを第２の目的とするものであ
る。 Furthermore, by using lithium halide as a flux to produce the phosphor, the firing temperature can be lowered.
The second objective is to provide a new manufacturing method suitable for crystal growth at temperatures below 1000°C.
前述の目的を達成するために本発明の低速電子
線用蛍光体は、一般式がZnO・Ga2O3で表わされ
る母体にLi及びｘをドープしたことを特徴とす
る。（但し、ｘはハロゲン元素）
また、Ga2O31molに対してZnOを0.5〜4.0mol
の割合で混合することが好ましい。
In order to achieve the above object, the low-speed electron beam phosphor of the present invention is characterized in that a matrix represented by the general formula ZnO.Ga 2 O 3 is doped with Li and x. (However, x is a halogen element) Also, 0.5 to 4.0 mol of ZnO per 1 mol of Ga 2 O 3
It is preferable to mix at a ratio of .
さらに、本発明の低速電子線用蛍光体の製造方
法として、ZnOとGa2O3とハロゲン化リチウムを
混合する工程と、混合物を耐火容器に入れ700〜
1000℃の焼成温度で１〜５時間加熱する工程を有
することを特徴とするものである。また、ハロゲ
ン化リチウムの混合量は0.05〜15mol％であるこ
とが好ましい。 Furthermore, the method for producing the phosphor for low-speed electron beams of the present invention includes a step of mixing ZnO, Ga 2 O 3 , and lithium halide, and a step of putting the mixture in a fireproof container and heating it for 700~
It is characterized by having a step of heating at a firing temperature of 1000°C for 1 to 5 hours. Further, the amount of lithium halide mixed is preferably 0.05 to 15 mol%.
本発明は、ZnOとGa2O3からZnO・Ga2O3母体
を形成させる工程で焼成温度を下げる作用をさせ
るためにハロゲン化リチウムを融剤として混合さ
せて蛍光体を比較的に低い温度で合成し、合成し
た蛍光体の結晶を分析したら、ハロゲン化リチウ
ムを0.05mol％未満混合させた場合はリチウムの
みが含まれていた。又、ハロゲン化リチウムを
0.05mol％以上混合させた場合はリチウム及びハ
ロゲン元素が含まれていた。このことからハロゲ
ン化リチウムは融剤の作用をする他にドナー成分
及びアクセプター成分として蛍光体中にドーピン
グされ、発光中心となる作用もしているのであ
る。たとえば、Clは母体中の０を置換してドナー
となり、Liは母体中のZn、Gaを置換するとアク
セプターとなる。また過剰にこれらをドープした
場合過剰のClは飛易いためドープされず、Liは母
体（ZnGa2O4）の格子間に位置し、ドナーとな
り、発光中心形成と同時に導電性をよくすること
になる。
In the present invention, lithium halide is mixed as a flux to lower the firing temperature in the process of forming a ZnO/Ga 2 O 3 matrix from ZnO and Ga 2 O 3 , and the phosphor is heated to a relatively low temperature. When we analyzed the crystals of the synthesized phosphor, we found that it contained only lithium when less than 0.05 mol% of lithium halide was mixed. Also, lithium halide
When mixed at 0.05 mol% or more, lithium and halogen elements were included. Therefore, in addition to acting as a flux, lithium halide is doped into the phosphor as a donor component and an acceptor component, and also functions as a luminescent center. For example, Cl replaces 0 in the matrix to become a donor, and Li replaces Zn and Ga in the matrix to become an acceptor. In addition, if these are doped excessively, the excess Cl tends to fly away, so it is not doped, and Li is located between the lattices of the matrix (ZnGa 2 O 4 ) and becomes a donor, forming a luminescent center and improving conductivity. Become.
蛍光体を合成するには、Ga2O31molに対し、
ZnOをAmol（但し、0.5≦Ａ≦4.0）とハロゲン化
リチウムを0.05〜15mol％加えて混合する。
Ga2O3の代わりにGaの硝酸塩、炭酸塩、硫酸塩
等で空気中で焼成して容易にGa2O3に変わる化合
物でもよい。また、ZnOの代わりにZnの硝酸塩、
炭酸塩、硫酸塩等で空気中で焼成して容易にZnO
に変わる化合物を酸化物に換算したときに、前述
の割合になるように混合してもよい。
To synthesize a phosphor, for 1 mol of Ga 2 O 3 ,
Amol of ZnO (however, 0.5≦A≦4.0) and 0.05 to 15 mol% of lithium halide are added and mixed.
Instead of Ga 2 O 3 , compounds such as Ga nitrates, carbonates, sulfates, etc. that can be easily converted into Ga 2 O 3 by firing in air may be used. Also, Zn nitrate instead of ZnO,
ZnO can be easily produced by firing in air with carbonate, sulfate, etc.
They may be mixed in such a manner that the above-mentioned proportions are obtained when converting the compound into an oxide.
さらに融剤としてLiCl（塩化リチウム）を0.05
〜15mol％加えてよく混合する。混合方法は、前
記材料をボールミル、ミキサー、乳鉢等を使用し
て充分混合を行う。 Additionally, add 0.05% LiCl (lithium chloride) as a fluxing agent.
Add ~15 mol% and mix well. The mixing method involves thoroughly mixing the above-mentioned materials using a ball mill, mixer, mortar, or the like.
混合物はアルミナボード等の耐熱容器に入れ、
空気中又は中性あるいは弱還元性雰囲気中で700
〜1000℃の温度で１〜５時間焼成して目的の蛍光
体を合成した。合成した蛍光体の結晶を純水で洗
浄して未反応のハロゲン化物を除去した。乾燥工
程を経て形成された蛍光体の結晶をオージエ分析
で分析したら、塩化リチウムの混合量よりLiのみ
が検出される場合とClのみが検出される場合と、
LiとClの両方が検出される場合があるので蛍光体
の結晶中にLiのみの場合とLi及びClがドープされ
ていることが証明された。しかし、Liのみが検出
されるのはLiClが0.05mol％未満を混合させた場
合であるが、この蛍光体は陽極電圧が100V以下
では輝度が低く、低速電子線用蛍光体としては利
用できないが、陽極電圧が高い条件であれば利用
できる。 Place the mixture in a heat-resistant container such as an alumina board.
700 in air or in a neutral or weakly reducing atmosphere
The desired phosphor was synthesized by baking at a temperature of ~1000°C for 1 to 5 hours. The synthesized phosphor crystals were washed with pure water to remove unreacted halides. When the phosphor crystals formed through the drying process are analyzed using Auger analysis, depending on the amount of lithium chloride mixed, sometimes only Li is detected, and sometimes only Cl is detected.
Since both Li and Cl may be detected in some cases, it has been proven that the phosphor crystal is doped with only Li or with Li and Cl. However, only Li is detected when less than 0.05 mol% of LiCl is mixed, but this phosphor has low brightness at an anode voltage of 100 V or less and cannot be used as a phosphor for slow electron beams. , it can be used as long as the anode voltage is high.
合成されたZnO・Ga2O3：Li，Cl蛍光体を有機
バインダーでペースト化して印刷法でガラス基板
の陽極導体上に被着させて、蛍光体の上方に制御
電極及びフイラメント状陰極を設け、側面板と前
面板からなる容器部で覆い、蛍光表示管を形成さ
せた。この蛍光表示管を陽極電圧80V、陰極電圧
が1.6Vに印加させて発光させたら、輝度は25〜
105ft―Ｌであり、発光色はすべて青色であつた。
また比較するために同一条件でLiClを混合しなか
つたものは、発光しきい値が80Vであり、陽極電
圧を100Vに上げても1ft―Ｌと低輝度であつた。 The synthesized ZnO・Ga 2 O 3 :Li, Cl phosphor is made into a paste with an organic binder and applied onto the anode conductor of a glass substrate using a printing method, and a control electrode and a filament-shaped cathode are provided above the phosphor. A fluorescent display tube was formed by covering the container with a container section consisting of a side plate and a front plate. If this fluorescent display tube emits light by applying an anode voltage of 80V and a cathode voltage of 1.6V, the brightness will be 25~
It was 105ft-L, and all the emitted light was blue.
For comparison, a device without LiCl mixed under the same conditions had a luminescence threshold of 80V, and even when the anode voltage was increased to 100V, the luminance was as low as 1ft-L.
そこでLiClの混合量と輝度の関係を調べた。 Therefore, we investigated the relationship between the amount of LiCl mixed and the brightness.
第３図は、LiClの混合量が変化すると輝度がど
のように変化するのかを調べた実験結果である。
AZnO・Ga2O3：Li，Cl蛍光体で、Ａ＝１になる
ようにZnOを4.1ｇとGa2O3を9.4ｇの条件に固定
し、融剤としてLiClを0.05mol％（0.01ｇ）、
0.5mol％（0.01ｇ）、3mol％（0.06ｇ）、5mol％
（0.1ｇ）10mol％（0.2ｇ）、15mol％（0.3ｇ）と
変化させて元した場合の６種類の蛍光体を空気中
で1000℃で２時間の焼成条件で合成した。そして
前記蛍光体を比較るためにLiClを入れてない場合
の従来のZnO・Ga2O3蛍光体を空気中で1000℃で
２時間の同一焼成条件で合成した。それらの蛍光
体を蛍光表示管に実装して、陰極電圧を1.6Vと
固定し、陽極電圧を０〜200Vまで変化させて印
加させたときの発光輝度を示したグラフである。 FIG. 3 shows the results of an experiment that investigated how the brightness changes when the amount of LiCl mixed changes.
AZnO・Ga 2 O 3 : Li, Cl phosphor, fixing 4.1 g of ZnO and 9.4 g of Ga 2 O 3 so that A=1, and adding 0.05 mol% (0.01 g of LiCl as a flux). ),
0.5mol% (0.01g), 3mol% (0.06g), 5mol%
(0.1 g), 10 mol% (0.2 g), and 15 mol% (0.3 g), six types of phosphors were synthesized under baking conditions at 1000° C. for 2 hours in air. In order to compare the phosphors, a conventional ZnO.Ga 2 O 3 phosphor without LiCl was synthesized under the same firing conditions at 1000° C. for 2 hours in air. This is a graph showing the luminance when these phosphors are mounted in a fluorescent display tube, the cathode voltage is fixed at 1.6V, and the anode voltage is varied from 0 to 200V.
LiClを5mol％混合した実施例が陽極電圧40V
以上で一番輝度が高く、次に3mol％、10mol％、
0.5mol％の順である。 The example in which 5 mol% of LiCl was mixed has an anode voltage of 40 V.
Above, the brightness is the highest, followed by 3mol%, 10mol%,
The order is 0.5 mol%.
次に第４図は、陽極電圧を100V、陰極電圧を
1.6Vで発光させた場合に一番高い輝度を100とし
た場合の相対輝度と、LiCl融剤の混合量の関係を
示すグラフである。このグラフからLiClの混合量
は0.05mol％〜15mol％の範囲が相対輝度で50以
上であり、蛍光表示管用として充分使用できる範
囲であることがわかる。中でも5mol％付近にピ
ークがあり一番高くなつている。 Next, in Figure 4, the anode voltage is 100V and the cathode voltage is 100V.
It is a graph showing the relationship between the relative brightness and the amount of LiCl flux mixed when the highest brightness is taken as 100 when emitting light at 1.6V. From this graph, it can be seen that when the amount of LiCl mixed is in the range of 0.05 mol % to 15 mol %, the relative brightness is 50 or more, which is a range that can be used sufficiently for fluorescent display tubes. Among them, there is a peak around 5 mol%, which is the highest.
次にGa2O31モルに対してZnOの混合するmol
数は、従来のＡ（Zn1-xMgx）Ｏ・Ga2O3蛍光体で
は、Ａで示され、その範囲は0.5≦Ａ≦1.2である
が、本発明のAZnO・Ga2O3：Li，Cl蛍光体のＡ
値は、どの範囲が良いか実験をした。予備実験と
してLiCl添加しない場合にGa2O3に対してZnOの
mol数を0.4、1.0、1.5、2.3、3.0、4.0と変化させ
た場合の蛍光体を合成した。すなわちＡ値を変化
させた蛍光体を陰極電圧1.6Vで陽極電圧を０〜
200Vまで変化させて印加した場合の輝度と陽極
電圧の関係は第５図に示すとおりである。陽極電
圧が100V以下では、Ａの値をどのようにしても
発光輝度は50ft―Ｌ以下と低い輝度であり、蛍光
表示管用としては輝度が低く使用できない。ま
た、Ａ値がある点より小さくても大きくても輝度
が低くなることがわかつた。そこで、陽極電圧
80Vで発光させた場合のGa2O31モルに対する
ZnOのmol数と、相対輝度の関係をグラフに示す
と第６図のようになる。このグラフからZnOのモ
ル数すなわちＡの値は1.5〜2.0の間にピークがあ
り、それ以上混合しても、またそれ以下に混合し
ても輝度が低下することがわかつた。 Next, mol of ZnO to be mixed for 1 mol of Ga 2 O 3
In the conventional A(Zn 1-x Mgx)O・Ga 2 O 3 phosphor, the number is indicated by A, and the range is 0.5≦A≦1.2, but in the AZnO・Ga 2 O 3 of the present invention: A of Li,Cl phosphor
We conducted an experiment to find out which range of values is best. As a preliminary experiment, we compared ZnO to Ga 2 O 3 without adding LiCl.
Fluorophores with different mol numbers of 0.4, 1.0, 1.5, 2.3, 3.0, and 4.0 were synthesized. In other words, the phosphors with different A values are used at a cathode voltage of 1.6V and an anode voltage of 0 to 0.
The relationship between the brightness and the anode voltage when varying up to 200V is shown in FIG. When the anode voltage is 100 V or less, the luminance is as low as 50 ft-L or less no matter what the value of A is, and the luminance is too low to be used for a fluorescent display tube. It was also found that the brightness decreases when the A value is smaller or larger than a certain point. Therefore, the anode voltage
For 1 mole of Ga 2 O 3 when emitting light at 80V
The relationship between the number of moles of ZnO and relative brightness is shown in a graph as shown in Figure 6. From this graph, it was found that the number of moles of ZnO, that is, the value of A, had a peak between 1.5 and 2.0, and that even if it was mixed more or less than that, the brightness decreased.
次に融剤のハロゲン化リチウムを加えた場合
に、Ａ値と輝度の関係を調べるために実験を行つ
た。LiClを5mol％に固定し、ZnOの混合量すな
わちＡ値を変化させることにより輝度の変化を測
定した。Ａ値を0.5、1.0、2.0、3.0、4.0、と変え
てZnOとGa2O3を混合し、それぞれにLiClを
5mol％混合した蛍光体を５種類合成して、蛍光
表示管に実装して、陰極電圧1.6V、陽極電圧80V
で発光させた。その結果、相対輝度とＡ値の関係
を示すグラフを第７図に示す。このグラフからも
わかるようにＡ値は0.5≦Ａ≦４の範囲が相対輝
度50％以上で、蛍光表示管用として充分使用でき
る輝度を有している。 Next, an experiment was conducted to examine the relationship between the A value and the brightness when lithium halide as a flux was added. LiCl was fixed at 5 mol %, and changes in brightness were measured by varying the amount of ZnO mixed, that is, the A value. Mix ZnO and Ga 2 O 3 with different A values of 0.5, 1.0, 2.0, 3.0, and 4.0, and add LiCl to each.
Five types of phosphors mixed at 5 mol% were synthesized and mounted in a fluorescent display tube, resulting in a cathode voltage of 1.6V and an anode voltage of 80V.
It was made to emit light. As a result, a graph showing the relationship between relative brightness and A value is shown in FIG. As can be seen from this graph, when the A value is 0.5≦A≦4, the relative luminance is 50% or more, and the luminance is sufficient for use as a fluorescent display tube.
次に、本発明のZnO・Ga2O3：Li，Cl蛍光体の
発光色について説明する。第８図にZnO・Ga2O3
の母体に対しLiClを15mol％混合した本発明の蛍
光体を実装した蛍光表示管の発光スペクトル図を
示す。このスペクトル図からピーク値は405nmに
あり、その半値幅は約360〜470nmの範囲である
ことから本発明の蛍光体は青色発光であることを
示している。 Next, the emission color of the ZnO.Ga 2 O 3 :Li,Cl phosphor of the present invention will be explained. Figure 8 shows ZnO・Ga 2 O 3
Fig. 3 shows an emission spectrum diagram of a fluorescent display tube equipped with the phosphor of the present invention in which 15 mol% of LiCl is mixed with the base material. This spectrum diagram shows that the peak value is at 405 nm and the half width is in the range of about 360 to 470 nm, which indicates that the phosphor of the present invention emits blue light.
また第９図は、CIEの色度座標であり、前記蛍
光体を実装した蛍光表示管の発光色度点を示すも
のである。同上蛍光体はｘ＝0.176、ｙ＝0.147の
色度点であり、色純度は85％と良好な値である。
さらに、この色度点の主波長は、473nmであり、
青色発光であることを示している。 Further, FIG. 9 shows CIE chromaticity coordinates, which indicate the emission chromaticity point of a fluorescent display tube in which the phosphor is mounted. The above phosphor has a chromaticity point of x=0.176 and y=0.147, and has a good color purity of 85%.
Furthermore, the dominant wavelength of this chromaticity point is 473 nm,
This indicates that it emits blue light.
なお、融剤の他の実施例としてLiFについて実
験を行つた。1.5ZnO・Ga2O3に融剤としてLiFを
5mol％添加混合して空気中で1000℃で２時間焼
成して蛍光体を合成した。 In addition, as another example of the fluxing agent, an experiment was conducted using LiF. 1.5ZnO・Ga 2 O 3 with LiF as a fluxing agent
A phosphor was synthesized by adding and mixing 5 mol % and baking in air at 1000°C for 2 hours.
前記合成した蛍光体を蛍光表示管に実装して陰
極電圧1.7V、陽極電圧を０〜200Vまで印加して
発光させて、各陽極電圧に対する輝度を測定した
ら次のような結果であつた。80Vで35ft―Ｌ、
90Vで44ft―Ｌ、100Vで51ft―Ｌであつた。LiF
は、LiClより輝度が低いが、従来のLi、ハロゲン
元素のドープ無しのZnO・Ga2O3蛍光体に比較し
て輝度が約５倍位高いので、ドープさせたLi及び
Ｆの効果が現われているものと考えられる。 The synthesized phosphor was mounted on a fluorescent display tube, and the cathode voltage was applied to 1.7V and the anode voltage was applied from 0 to 200V to emit light.The luminance at each anode voltage was measured, and the following results were obtained. 35ft-L at 80V,
It was 44ft-L at 90V and 51ft-L at 100V. LiF
Although the brightness is lower than that of LiCl, the brightness is about five times higher than that of conventional ZnO・Ga 2 O 3 phosphors that are not doped with Li or halogen elements, so the effect of doped Li and F appears. It is thought that the
次に本発明のZnO・Ga2O3：Lix（ｘはハロゲン
元素）の焼成条件は、空気中又は弱酸化雰囲気中
で焼成させ、母体金属以外にハロゲン化リチウム
を融剤して使用するので、融剤を使用しない従来
の焼成温度以下で焼成することが可能となり、焼
成温度は800〜1000℃である。焼成時間は１〜５
時間であつた。 Next, the firing conditions for ZnO・Ga 2 O 3 :Lix (x is a halogen element) of the present invention are that it is fired in air or in a weakly oxidizing atmosphere, and lithium halide is used as a flux in addition to the base metal. , it is now possible to fire at a temperature lower than the conventional firing temperature without using a flux, and the firing temperature is 800 to 1000°C. Baking time is 1-5
It was time.
また、雰囲気が中性又は弱還元性雰囲気中で焼
成させる場合も同様にハロゲン化リチウムを融剤
として使用するので700〜900℃の焼成温度で２〜
５時間の焼成時間で本発明の蛍光体が合成でき
た。 Also, when firing in a neutral or weakly reducing atmosphere, lithium halide is similarly used as a flux, so the firing temperature is 700 to 900°C.
The phosphor of the present invention was synthesized in a firing time of 5 hours.
本発明は、以上述べたように、母体となる
ZnO・Ga2O3に付活剤及び融剤としてのハロゲン
化リチウムを所定量混合した後焼成工程を経て
ZnO・Ga2O3：LiX（但し、ｘはハロゲン元素）
蛍光体が得られたので次に述べるような効果を有
する。
As described above, the present invention is based on
After mixing a predetermined amount of lithium halide as an activator and flux with ZnO・Ga 2 O 3 , it undergoes a firing process.
ZnO・Ga 2 O 3 :LiX (however, x is a halogen element)
Since the phosphor was obtained, it has the following effects.
(1) 本発明のZnO・Ga2O3：Li，ｘ蛍光体はLi及
びハロゲン元素ドーピングさせたので100V以
下の陽極電圧でも100ft―Ｌ前後と高く、蛍光
表示管用の青色蛍光体としても充分使用でき、
カラー蛍光表示管の利用拡大に結び付く。(1) Since the ZnO・Ga 2 O 3 :Li,x phosphor of the present invention is doped with Li and halogen elements, it is as high as around 100 ft-L even at an anode voltage of 100 V or less, and is sufficient as a blue phosphor for fluorescent display tubes. can be used,
This will lead to expanded use of color fluorescent display tubes.
(2) 本発明のZnO・Ga2O3：Li，ｘ蛍光体には、
硫化物を含有していない酸化物系蛍光体である
ので、蛍光表示管に実装して発光させても、硫
化物系ガスの飛散という現象も起らず、エミツ
シヨン特性を劣化させることが皆無になり、長
寿命の信頼性の高い蛍光表示管を提供できる効
果を有する。(2) The ZnO・Ga 2 O 3 :Li,x phosphor of the present invention has
Since it is an oxide-based phosphor that does not contain sulfides, even if it is mounted in a fluorescent display tube and emitted light, sulfide-based gas will not scatter and there will be no deterioration of the emission characteristics. This has the effect of providing a highly reliable fluorescent display tube with a long life.
(3) 蛍光体の製造方法において、ハロゲン化リチ
ウムを融剤として作用させたので、焼成温度を
従来に比較して低い温度で焼成することにより
本発明の蛍光体を得ることが可能となり、熱効
率をよくすると共に、結晶成長に適した温度と
なり、結晶状態の良好な蛍光体が得られるとい
う効果を有する。(3) In the method for producing the phosphor, lithium halide is used as a fluxing agent, so the phosphor of the present invention can be obtained by firing at a lower firing temperature than conventional methods, resulting in improved thermal efficiency. This has the effect of improving the temperature, making the temperature suitable for crystal growth, and obtaining a phosphor with a good crystalline state.
第１図は、一般的な蛍光表示管の一部を破断し
た平面図、第２図は、第１図の要部の拡大断面
図、第３図は、本発明の蛍光体でLiClの混合量を
変えた場合の発光輝度と陽極電圧の関係を示すグ
ラフ、第４図は、陽極電圧100Vの場合のLiClの
混合量と相対発光輝度を示すグラフ、第５図は、
融剤を入れないZnO・Ga2O3蛍光体においてZnO
の混合量を変えた場合の陽極電圧と輝度の関係を
示すグラフ、第６図は、融剤を入れないZnO・
Ga2O3蛍光体において陽極電圧を80Vで発光させ
た場合のZnOの混合量と相対輝度の関係を示すグ
ラフ、第７図は、本発明の蛍光体で陽極電圧80V
で発光させた場合のZnOの混合量と相対輝度の関
係を示すグラフ、第８図は、本発明の蛍光体の発
光スペクトル図、第９図は、同蛍光体及び従来の
ZnO・Ga2O3蛍光体を示すCIE色度図である。
Fig. 1 is a partially cutaway plan view of a general fluorescent display tube, Fig. 2 is an enlarged sectional view of the main part of Fig. 1, and Fig. 3 is a mixture of LiCl with the phosphor of the present invention. A graph showing the relationship between luminescence brightness and anode voltage when the amount is changed. Figure 4 is a graph showing the amount of LiCl mixed and relative luminance when the anode voltage is 100V. Figure 5 is a graph showing the relationship between the amount of LiCl mixed and the anode voltage.
ZnO in ZnO・Ga 2 O 3 phosphor without fluxing agent
Figure 6 is a graph showing the relationship between anode voltage and brightness when the mixing amount of ZnO is changed.
Figure 7 is a graph showing the relationship between the amount of ZnO mixed and the relative brightness when the Ga 2 O 3 phosphor emits light at an anode voltage of 80V.
Figure 8 is an emission spectrum diagram of the phosphor of the present invention, and Figure 9 is a graph showing the relationship between the amount of ZnO mixed and relative brightness when emitting light.
FIG. 2 is a CIE chromaticity diagram showing a ZnO.Ga 2 O 3 phosphor.
Claims (1)
及びｘをドープしたことを特徴とする低速電子線
用蛍光体。（但し、ｘはＦ、Cl、Br、Ｉ等から選
ばれた少なくとも１種のハロゲン元素）。 ２ Ga2O31molに対してZnOのmol数が0.5〜
4.0molである特許請求の範囲第１項記載の低速
電子線用蛍光体。 ３ ZnOとGa2O3とハロゲン化リチウムを混合す
る工程と、混合物を耐火性容器に入れ700〜1000
℃の焼成温度で１〜５時間加熱する工程を有する
ことを特徴とする低速電子線用蛍光体の製造方
法。 ４ ハロゲン化リチウムの混合量が0.05〜15mol
％である特許請求の範囲第３項記載の低速電子線
用蛍光体の製造方法。[Claims] 1 Li in the matrix whose general formula is ZnO・Ga 2 O 3
and x-doped phosphor for low-speed electron beams. (However, x is at least one halogen element selected from F, Cl, Br, I, etc.). 2 The number of moles of ZnO is 0.5 to 1 mole of Ga 2 O 3
The phosphor for slow electron beams according to claim 1, which has a concentration of 4.0 mol. 3 The process of mixing ZnO, Ga 2 O 3 and lithium halide, and placing the mixture in a fireproof container for 700 to 1000
A method for producing a phosphor for low-speed electron beams, comprising a step of heating at a firing temperature of 1 to 5 hours. 4 Mixed amount of lithium halide is 0.05 to 15 mol
% of the phosphor for low-speed electron beams according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8926286A JPS62243679A (en) | 1986-04-17 | 1986-04-17 | Fluorescent substance for slow electon ray and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8926286A JPS62243679A (en) | 1986-04-17 | 1986-04-17 | Fluorescent substance for slow electon ray and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62243679A JPS62243679A (en) | 1987-10-24 |
| JPH0260706B2 true JPH0260706B2 (en) | 1990-12-18 |
Family
ID=13965841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8926286A Granted JPS62243679A (en) | 1986-04-17 | 1986-04-17 | Fluorescent substance for slow electon ray and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62243679A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0747733B2 (en) * | 1988-12-28 | 1995-05-24 | 双葉電子工業株式会社 | Blue light emitting phosphor |
| JP2001107040A (en) * | 1999-10-04 | 2001-04-17 | Futaba Corp | Phosphor and fluorescent display tube |
-
1986
- 1986-04-17 JP JP8926286A patent/JPS62243679A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62243679A (en) | 1987-10-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |