JPH0386785A - Production of zns:cu phosphor - Google Patents
Production of zns:cu phosphorInfo
- Publication number
- JPH0386785A JPH0386785A JP1221568A JP22156889A JPH0386785A JP H0386785 A JPH0386785 A JP H0386785A JP 1221568 A JP1221568 A JP 1221568A JP 22156889 A JP22156889 A JP 22156889A JP H0386785 A JPH0386785 A JP H0386785A
- Authority
- JP
- Japan
- Prior art keywords
- zns
- powder
- hcl
- phosphor
- atmosphere
- 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.)
- Granted
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 4
- 230000001502 supplementing effect Effects 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000005401 electroluminescence Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はＺｎＳ ： Ｃｕ系蛍光体粉末の製造方法に関
する。詳しくは、優れた発光効率及び輝度を有し、交流
エレクトロルミネッセンス（ＥＬ）発光素子に適した２
０〜５０μｍの比較的大粒径のＺｎＳ ： Ｃｕ系蛍光
体粉末の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing ZnS:Cu-based phosphor powder. Specifically, it has excellent luminous efficiency and brightness, and is suitable for AC electroluminescence (EL) light emitting elements.
The present invention relates to a method for producing ZnS:Cu-based phosphor powder having a relatively large particle size of 0 to 50 μm.
ＺｎＳ ： Ｃｕ系蛍光体粉末の製造方法としては、従
来ＺｎＳ生粉と酢酸銅（（ＣＨ，Ｃ００）、Ｃｕ）等Ｃ
ｕイオン含有化合物水溶液とＮａＣｎ、Ｋｌｊｌ、 Ｎ
Ｈ４Ｃｌ等のハロゲン化物（フラックス）の水溶液とを
混和・乾燥し不活性ガスあるいはＨ２Ｓ、 Ｃ５２等の
硫化性ガス雰囲気中で焼成する方法が行なわれている。ZnS: The conventional method for manufacturing Cu-based phosphor powder is to use ZnS raw powder and copper acetate ((CH,C00), Cu), etc.
U ion-containing compound aqueous solution and NaCn, Kljl, N
A method is used in which the mixture is mixed with an aqueous solution of a halide (flux) such as H4Cl, dried, and fired in an atmosphere of an inert gas or a sulfidic gas such as H2S or C52.
また最近、前記の方法で作成された蛍光体粉末を空気中
で再焼成し、生じたＺｎＯをエツチングで除去する方法
（特開昭５８−１２３６９３号）、焼成されたＺｎＳ
： Ｃｕ系の蛍光体にＣｕ化合物を添加混合して、空気
中で高温で再焼成する方法（特開昭６２−６１２９４号
）等が提案されている。Recently, a method (Japanese Unexamined Patent Publication No. 123693/1983) in which the phosphor powder produced by the above method is re-fired in air and the resulting ZnO is removed by etching,
: A method has been proposed in which a Cu compound is added to and mixed with a Cu-based phosphor and re-baked in air at a high temperature (Japanese Patent Laid-Open No. 62-61294).
しかしながら、前記の諸方法では何れもＫＣＲｌＮａＣ
ｆｌ、 ＮＨ４Ｃｌ１等を含有し、粒成長させる為に１
１００〜１２００℃という高い温度で焼結させなければ
ならず、高温型のα−ＺｎＳが副成するため充分な発光
効率と輝度を有する蛍光体粉末を得ることは難しい。However, in all of the above methods, KCRlNaC
Contains fl, NH4Cl1, etc., and 1 for grain growth.
It is difficult to obtain a phosphor powder with sufficient luminous efficiency and brightness because it must be sintered at a high temperature of 100 to 1200°C, and high-temperature α-ZnS is formed as a by-product.
また蛍光体として使用するためには発光効率と輝度の大
きな低温型のβ−ＺｎＳであっである程度大きな粒径の
焼結体とすることが必要であるが、低温型焼結体を得る
目的で従来の製造法の焼結温度を下げると蛍光体に必要
な大きさの粒を得ることができない。In addition, in order to use it as a phosphor, it is necessary to make a sintered body of low-temperature type β-ZnS with high luminous efficiency and brightness and a somewhat large particle size. If the sintering temperature of conventional manufacturing methods is lowered, it is not possible to obtain grains of the size required for the phosphor.
従来の上記問題を解決するためには、 Ｋ、Ｎａ、ＮＨ
。In order to solve the above conventional problems, K, Na, NH
.
等の使用を極力排除し、結晶性のよい蛍光体粉末を作り
出すことが必要である。It is necessary to eliminate the use of such substances as much as possible and create a phosphor powder with good crystallinity.
本発明者らの第一の着眼点は、蛍光体粉末の粒成長に従
来（１）ＫＣＱ、 ＮａＣｌ２、ＮＨ４ＣＱなどを使用
することなく、次の式（１）
％式％（１）
で表わされる平衡反応を利用することである。この平衡
は１２０℃付近を境界としてそれ以下の温度では式（１
）の右から左へ、１２０℃付近より高い温度では左から
右へ移行することが知られている。そこで第二の着眼点
としてまず常温付近でＺｎｃ１２２を生成させた後、系
の温度を上げてＺｎ５粒を生長させ、焼成した後Ｈ２Ｓ
ｌ囲気中で冷却することにより、発光特性が高く１粒生
長して大粒径の低温型β−ＺｎＳ蛍光体粉末を得ようと
するものである。The first point of focus of the present inventors is that (1) KCQ, NaCl2, NH4CQ, etc. are not conventionally used for grain growth of phosphor powder, and the growth can be expressed by the following formula (1) % formula % (1) It is the use of equilibrium reactions. This equilibrium has a boundary around 120℃, and at lower temperatures, the equation (1
) is known to shift from right to left at temperatures higher than around 120°C. Therefore, the second point of focus is to first generate Znc122 at room temperature, then increase the temperature of the system to grow Zn5 grains, and after firing, H2S
The purpose is to obtain a low-temperature type β-ZnS phosphor powder with high luminescent properties and single grain growth and large grain size by cooling in an ambient atmosphere.
本発明は、Ｃｕを０．０５〜０．５０ｗｔ％含有するＺ
ｎＳ粉末を、１２０℃以下でＨＣｌまたはＨ２ＳとＩＩ
ＣＱとの混合雰囲気下におき、７５０〜１０２０’Ｃに
昇温して１１２８を補充しながら焼成した後、Ｈ２Ｓ１
囲気中で冷却することを特徴とするＺｎＳ ： Ｃｕ系
蛍光体粉末の製造方法を提供する。The present invention is directed to Z containing 0.05 to 0.50 wt% of Cu.
nS powder with HCl or H2S at below 120°C
Placed in a mixed atmosphere with CQ, heated to 750-1020'C, and fired while supplementing 1128, H2S1
Provided is a method for producing ZnS:Cu-based phosphor powder, which is characterized by cooling in an ambient atmosphere.
本発明に用いられるＺｎＳ粉末のＣｕ含有量は、０．０
５〜０．５０ｗｔ％である。 Ｃｕが０．０５ｗｔ％以
下では発光中心の形成が不十分で輝度が上がらない。ま
た、Ｃｕが０．５０すｔ％より多くなると濃度消光が起
って輝度が低下するｍ ＺｎＳにＣｕを含有させるには
Ｃｕイオン含有溶液にＺｎＳ粉末を加えて混和・乾燥す
る公知の方法が用いられる。 Ｃｕ源としてはＣｕ塩が
用いられるが、なかでも焼成後に残留しない有機酸塩が
好ましく、（ＣＨ，Ｃ００）２Ｃｕは特に好適である。The Cu content of the ZnS powder used in the present invention is 0.0
It is 5 to 0.50 wt%. If Cu is less than 0.05 wt%, the formation of luminescent centers will be insufficient and the brightness will not increase. In addition, when Cu exceeds 0.50 t%, concentration quenching occurs and the brightness decreases.To incorporate Cu into ZnS, a known method is to add ZnS powder to a Cu ion-containing solution, mix and dry. used. A Cu salt is used as the Cu source, but organic acid salts that do not remain after firing are preferred, and (CH,C00)2Cu is particularly preferred.
本発明は前記のＺｎＳ ： Ｃｕ粉末を原料とし５式（
１）％式％（１）
に示される平衡反応系を利用してＺｎＳの粒成長ｉさせ
る。この平衡反応系は１２０℃付近以下の温度領域では
式（１）の左側に、１２０℃付近以上の温度領域では右
側に移行する。The present invention uses the above-mentioned ZnS:Cu powder as a raw material and uses the formula 5 (
1) ZnS grains are grown using the equilibrium reaction system shown in the formula (1). This equilibrium reaction system shifts to the left side of equation (1) in a temperature range of around 120°C or lower, and to the right side in a temperature range of around 120°C or higher.
そこで本発明では、第１段階としてＺｎ ： Ｃｕ系粉
末をＨＣｆｌガス雰囲気中で１２０℃以下にしてその表
面にＺｎＣＱ２を形成し、次いで第２段階として、Ｈ１
ＳガスでＨＣｌガスを一部置換えした雰囲気中でＨ２Ｓ
を補充しながら７５０℃〜１０２０℃にして該Ｚｎ５Ｓ
Ｃｕ系粉末を焼成させ、引き続きＨ２Ｓ雰囲気下で冷却
する。Therefore, in the present invention, as a first step, Zn:Cu-based powder is heated to 120°C or lower in an HCfl gas atmosphere to form ZnCQ2 on its surface, and then as a second step, H1
H2S in an atmosphere in which HCl gas is partially replaced with S gas.
The Zn5S was heated to 750°C to 1020°C while replenishing
The Cu-based powder is fired and subsequently cooled under an H2S atmosphere.
第１段階および第２段階を通じてＨＣｌとＨ２Ｓの混合
ガスを用いれば、ガスの入れ換えがなく製造が容易であ
る。また第２段階の焼成時にはＨ２Ｓと同時にＩＩＣＱ
が存在しないと反応が良好に進まない、Ｈ２ＳとＨＣｌ
の混合ガスを用いる場合Ｈ２Ｓ ： ＨＣｌの比が３０
〜９５ ： ７０〜５の範囲であることが好ましい、Ｈ
２Ｓ：ＨＣｆｆ＝３０ ： ７０よりＨ２Ｓが少ないと
焼成時に充分な粒生長が起らず、またＨＣｌが）ｌ、Ｓ
： ＨＣｌ１＝９５：５よりも少ないと発光中心の形
成が不十分で蛍光体の輝度が上がらない。If a mixed gas of HCl and H2S is used in the first and second stages, there is no need to replace the gas and the production is easy. In addition, at the second stage of firing, IICQ is used at the same time as H2S.
In the absence of H2S and HCl, the reaction does not proceed well.
When using a mixed gas of H2S: HCl ratio of 30
~95: preferably in the range of 70 to 5, H
2S:HCff=30: If H2S is less than 70, sufficient grain growth will not occur during firing, and HCl)
: If HCl1 is less than 95:5, the luminescent center will not be formed sufficiently and the brightness of the phosphor will not increase.
焼成時には式（１）の平衡は右側に移行し、Ｈ２Ｓを消
費しなからＺｎＳの粒生長が起るため雰囲気中のＨ２Ｓ
を逐次補充することが必要である。During firing, the equilibrium of equation (1) shifts to the right, and grain growth of ZnS occurs without consuming H2S, so H2S in the atmosphere
It is necessary to replenish it sequentially.
本発明における焼成温度は７５０〜１０２０℃の範囲で
ある。７５０℃以下ではＺｎＳの粒成長が起らない。The firing temperature in the present invention is in the range of 750 to 1020°C. ZnS grain growth does not occur below 750°C.
これはＺｎ（ｊｌ＊の沸点が７３０℃であることに由来
する。This is because the boiling point of Zn (jl*) is 730°C.
また１０２０℃より高い温度で焼成すると、高温型のα
型ＺｎＳの副成が進み発光効率が低下すると共に。Also, if fired at a temperature higher than 1020℃, high-temperature type α
As the sub-formation of ZnS type progresses, the luminous efficiency decreases.
粒成長が進み過ぎて１００μｍ以上となり、ＥＬ発光素
子に適した２０〜５０μ重の粒径に比較して過大となる
ため好ましくない、Ｈ２Ｓを補充し乍ら前記温度範囲で
焼成することにより低温β型ＺｎＳを主体とする蛍光体
粉末を得ることができる。Grain growth progresses too much to 100 μm or more, which is undesirable as it becomes too large compared to the grain size of 20 to 50 μm suitable for EL light emitting devices. A phosphor powder mainly composed of type ZnS can be obtained.
焼成終了後、更にＨ２Ｓを導入しながら冷却する。After the firing, the mixture is further cooled while introducing H2S.
Ｈ２Ｓ雰囲気中で冷却すれば１２０℃以下を温まで温度
を下げてもＺｎＣＱ、を生成しない。得られた粉末は公
知の方法によりＨＣｌ水溶液、 ＮａＣＮ水溶液で洗浄
した後十分に水洗・乾燥してＺｎＳ ： Ｃｕ蛍光体が
得られる。If it is cooled in an H2S atmosphere, ZnCQ will not be produced even if the temperature is lowered to below 120°C. The obtained powder is washed with an aqueous HCl solution and an aqueous NaCN solution by a known method, and then sufficiently washed with water and dried to obtain a ZnS:Cu phosphor.
本発明の方法を用いれば、優れた発光効率および輝度を
有し、２０〜５０μｍの比較的大粒径の交流ＥＬ素子に
適したＺｎＳ：Ｃｕ蛍光体粉末を容易に得ることができ
る。By using the method of the present invention, it is possible to easily obtain a ZnS:Cu phosphor powder that has excellent luminous efficiency and brightness and is suitable for AC EL devices with a relatively large particle size of 20 to 50 μm.
ＺｎＳ生粉に（ＣＨ，Ｃ００）２Ｃｕ水溶液を混和・乾
燥してＺｎＳに対するＣｎ含有量が０．１ｗｔ％である
原料を得た。A (CH,C00)2Cu aqueous solution was mixed with ZnS raw powder and dried to obtain a raw material with a Cn content of 0.1 wt% relative to ZnS.
このＺｎＳ ： Ｃｕ粉末７０ｇを石英ボー′トに秤取
し、５５φＸ１４００ｍ＋（赤熱部８００ｎｍ）の管状
炉に仕込んだ、この管状炉にＩ＋、ＳとＨＣｌとを６５
： ３５の比となるように導入し系内を完全に置換し
た。ガスの供給を止めて９５０℃に昇温し、Ｈ２Ｓを補
充しながら該温度で１時間焼成し、更にＨ２Ｓを補充し
ながら冷却した。70g of this ZnS:Cu powder was weighed into a quartz boat and charged into a 55φ x 1400m+ (red-hot part: 800nm) tube furnace.
:35 to completely replace the system. The gas supply was stopped and the temperature was raised to 950° C., and the mixture was fired at this temperature for 1 hour while replenishing H2S, and then cooled while replenishing H2S.
得られた粉末を、２Ｎ−ＨＣｌと３％ＮａＣＮ水溶液で
洗浄した後十分に水洗・乾燥してＺｎＳ ： Ｃｕ蛍光
体（Ａ）を得た。The obtained powder was washed with 2N-HCl and 3% NaCN aqueous solution, and then sufficiently washed with water and dried to obtain a ZnS:Cu phosphor (A).
比較のため、Ｃｕを０．ｌｗｔ％含有するＺｎＳ粉末に
ＺｎＳの１０％のＮＨ４Ｃｌを混和し全体で７７ｇとし
たものを石英るつぼに仕込み、雰囲気炉を用いて窒素雰
囲気中で１０７５℃で一時間焼成し、同様の処理を行っ
て、ＺｎＳ ： Ｃｕ蛍光体（Ｂ）を得た。For comparison, Cu was 0. A total of 77 g of ZnS powder containing 1 wt% of ZnS mixed with 10% of NH4Cl was charged into a quartz crucible, fired at 1075°C for 1 hour in a nitrogen atmosphere using an atmospheric furnace, and subjected to the same treatment. Thus, a ZnS:Cu phosphor (B) was obtained.
常法により、この二つの粉末を交流１セルに組み立て、
４００ Ｈｚの交流動作により発光させたところ、電位
−発光曲線は 図に示す通りであり、明らかに、本発明
の蛍光粉末について輝度及び発光特性の改善が認められ
た。Assemble these two powders into one AC cell using the usual method,
When the fluorescent powder of the present invention was emitted by AC operation at 400 Hz, the potential-emission curve was as shown in the figure, and it was clearly observed that the fluorescent powder of the present invention had improved brightness and emission characteristics.
図は本発明の実施例および比較例で得たＺｎＳ ：Ｃｕ
蛍光体（Ａ）および（Ｂ）を交流ＥＬセルに組立てて発
光させた電位−発光曲線である（４００ｔ（ｚ）。The figure shows ZnS:Cu obtained in Examples and Comparative Examples of the present invention.
This is a potential-emission curve obtained by assembling phosphors (A) and (B) into an AC EL cell and emitting light (400t(z)).
Claims (2)
末を、１２０℃以下でＨＣｌまたはＨ＿２ＳとＨＣｌと
の混合雰囲気下におき、７５０〜１０２０℃に昇温して
Ｈ＿２Ｓを補充しながら焼成した後、Ｈ＿２Ｓ雰囲気中
で冷却することを特徴とするＺｎＳ：Ｃｕ系蛍光体粉末
の製造方法。1. ZnS powder containing 0.05 to 0.50 wt% of Cu is placed in an atmosphere of HCl or a mixture of H_2S and HCl at 120°C or lower, heated to 750 to 1020°C, and fired while replenishing H_2S. , a method for producing a ZnS:Cu-based phosphor powder, characterized by cooling in an H_2S atmosphere.
て、Ｈ＿２Ｓ：ＨＣｌの比が３０〜９５：７０〜５であ
る請求項１記載のＺｎＳ：Ｃｕ系蛍光体粉末の製造方法
。2. The method for producing ZnS:Cu-based phosphor powder according to claim 1, wherein when a mixed gas of H_2S and HCl is used, the ratio of H_2S:HCl is 30-95:70-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1221568A JP2586147B2 (en) | 1989-08-30 | 1989-08-30 | Method for producing ZnS: Cu-based phosphor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1221568A JP2586147B2 (en) | 1989-08-30 | 1989-08-30 | Method for producing ZnS: Cu-based phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0386785A true JPH0386785A (en) | 1991-04-11 |
| JP2586147B2 JP2586147B2 (en) | 1997-02-26 |
Family
ID=16768772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1221568A Expired - Lifetime JP2586147B2 (en) | 1989-08-30 | 1989-08-30 | Method for producing ZnS: Cu-based phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2586147B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5269966A (en) * | 1992-12-31 | 1993-12-14 | Osram Sylvania Inc. | Method of making zinc sulfide precursor material for a copper-activated zinc sulfide electroluminescent phosphor |
-
1989
- 1989-08-30 JP JP1221568A patent/JP2586147B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5269966A (en) * | 1992-12-31 | 1993-12-14 | Osram Sylvania Inc. | Method of making zinc sulfide precursor material for a copper-activated zinc sulfide electroluminescent phosphor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2586147B2 (en) | 1997-02-26 |
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