JPH0782553A - Infrared luminescent material - Google Patents
Infrared luminescent materialInfo
- Publication number
- JPH0782553A JPH0782553A JP5254897A JP25489793A JPH0782553A JP H0782553 A JPH0782553 A JP H0782553A JP 5254897 A JP5254897 A JP 5254897A JP 25489793 A JP25489793 A JP 25489793A JP H0782553 A JPH0782553 A JP H0782553A
- Authority
- JP
- Japan
- Prior art keywords
- light emitting
- emitting material
- light
- luminescent material
- emission
- 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.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 9
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- -1 neodymium ions Chemical class 0.000 description 6
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 241000255964 Pieridae Species 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-H [oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O YDHWWBZFRZWVHO-UHFFFAOYSA-H 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は発光材料に関する。更に
詳細には、本発明はネオジムイオン（Ｎｄ3+）で賦活さ
れた赤外発光材料に関する。FIELD OF THE INVENTION This invention relates to luminescent materials. More specifically, the present invention relates to infrared emitting materials activated with neodymium ions (Nd 3+ ).
【０００２】[0002]
【従来の技術】近年、蛍光体を用いて郵便物にマークを
付したり、例えば、バーコードなどにより必要な情報を
所定の用紙に記録したりして、蛍光体マークからの発光
のみを蛍光体の励起波長に合致した励起光源で照射し
て、マーク部分を選択的に検出し、この検出によって郵
便物を仕分けたり、用紙に記録された情報を光学的カー
ドリーダーなどで正確に読み取ることが行われている。2. Description of the Related Art In recent years, a fluorescent substance is used to mark a postal matter, or necessary information is recorded on a predetermined sheet by, for example, a bar code so that only the light emitted from the fluorescent substance mark is fluorescent. By irradiating with an excitation light source that matches the excitation wavelength of your body, you can selectively detect the mark part, and by this detection you can sort mail items and accurately read the information recorded on paper with an optical card reader etc. Has been done.
【０００３】この方式によれば、情報を記録する有色
（例えば、黒色）インクを用いたバーコードと異なり、
記録されたマークがある場合にのみ蛍光信号を検出する
ために、励起光源の反射光は無視でき、原理的にコント
ラスト比は高くなり、読取誤動作が少なくなると考えら
れている。According to this method, unlike a bar code using a colored (for example, black) ink for recording information,
Since the fluorescence signal is detected only when there is a recorded mark, it is considered that the reflected light of the excitation light source can be ignored, the contrast ratio is increased in principle, and the reading malfunction is reduced.
【０００４】従来、光学的マーキング用発光材料として
は、ネオジムイオン（Ｎｄ3+）で賦活された波長１０５
０ｎｍ付近に大きな発光ピークを示す赤外発光材料、例
えば、ＬｉＮｄＰ4 Ｏ12などが知られていた。光学的マ
ーキングにおいては、発光材料によりマーキングを施し
た媒体を、発光材料の励起波長に合致した発光スペクト
ルを有する励起光源で照射し、発光材料からの発光のみ
を選択的に検出することにより、媒体に記録された情報
を正確に読み取ることが可能である。特に、ＬｉＮｄＰ
4 Ｏ12発光材料を用いることの利点の一つは、吸収およ
び発光イオンであるネオジムイオンの赤外における吸収
断面積が大きいので、発光材料層を薄くしても情報の読
取が可能なことであった。Conventionally, as a light emitting material for optical marking, a wavelength 105 activated by neodymium ion (Nd 3+ ) has been used.
An infrared light emitting material showing a large light emission peak near 0 nm, such as LiNdP 4 O 12 has been known. In optical marking, a medium marked with a luminescent material is irradiated with an excitation light source having an emission spectrum matching the excitation wavelength of the luminescent material, and only the luminescence from the luminescent material is selectively detected to obtain the medium. It is possible to accurately read the information recorded in. In particular, LiNdP
One of the advantages of using a 4 O 12 luminescent material is that since the absorption and emission absorption neodymium ions have a large absorption cross section in the infrared, it is possible to read information even if the luminescent material layer is thin. there were.
【０００５】しかしながら、従来のネオジム賦活発光材
料の発光出力は比較的低く、光学的マーキング用、特に
カードリーダ用として必ずしも満足できるものではなか
った。However, the conventional neodymium-activated light emitting material has a relatively low light emission output, which is not always satisfactory for optical marking, particularly for card readers.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明の目的
は、波長１０５０ｎｍ付近で高い発光出力を有するネオ
ジム賦活発光材料を提供することである。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a neodymium-activated light emitting material having a high light emission output near a wavelength of 1050 nm.
【０００７】[0007]
【課題を解決するための手段】前記目的を達成するため
に、本発明では、下記の一般式、 ＡＢx Ｎｄ1-x Ｐ4 Ｏ12 （式中、ＡはＬｉ，ＮａおよびＫからなる群から選択さ
れる少なくとも一種類以上のアルカリ金属元素であり、
ＢはＳｂ，Ｌｕ，Ｇａ，Ｓｃ，Ｙ，Ｌａ，Ｃｅ，Ｇｄ，
Ｉｎ，Ｂｉ，ＡｌおよびＴｌからなる群から選択される
少なくとも一種類以上の三価のイオンとなりうる金属元
素であり、０．０５≦ｘ≦０．８である）で示される組
成を有することを特徴とする赤外発光材料を提供する。In order to achieve the above object, the present invention provides the following general formula: AB x Nd 1-x P 4 O 12 (wherein A is a group consisting of Li, Na and K). Is at least one or more alkali metal elements selected from,
B is Sb, Lu, Ga, Sc, Y, La, Ce, Gd,
A metal element capable of forming at least one kind of trivalent ion selected from the group consisting of In, Bi, Al and Tl, and having a composition represented by 0.05 ≦ x ≦ 0.8). A featured infrared light emitting material is provided.
【０００８】[0008]
【作用】前記のように、ネオジム賦活発光材料、ＡＮｄ
Ｐ4 Ｏ12（但し、ＡはＬｉ，ＮａおよびＫからなる群か
ら選択される少なくとも一種類以上のアルカリ金属元素
である）において、発光中心であるネオジムイオン（Ｎ
ｄ3+）の一部をＳｂ，Ｌｕ，Ｇａ，Ｓｃ，Ｙ，Ｌａ，Ｃ
ｅ，Ｇｄ，Ｉｎ，Ｂｉ，ＡｌおよびＴｌからなる群から
選択される少なくとも一種類以上の三価のイオン、例え
ば、ガドリニウムイオン（Ｇｄ3+）および／またはイッ
トリウムイオン（Ｙ3+）によって置換することにより、
波長１０５０ｎｍ付近において従来の発光材料よりも大
きな発光出力を有する発光材料を提供することができ
る。As described above, the neodymium-activated luminescent material, ANd
In P 4 O 12 (where A is at least one or more alkali metal elements selected from the group consisting of Li, Na and K), the neodymium ion (N
d 3+ ) part of Sb, Lu, Ga, Sc, Y, La, C
Substituted by at least one or more trivalent ions selected from the group consisting of e, Gd, In, Bi, Al and Tl, for example, gadolinium ion (Gd 3+ ) and / or yttrium ion (Y 3+ ). By
It is possible to provide a light emitting material having a larger light emission output than a conventional light emitting material in the vicinity of a wavelength of 1050 nm.
【０００９】本発明の発光材料は、基本的にＮｄの４ｆ
電子の４ｆ−４ｆ遷移により発光するものであるが、従
来の発光材料に比べて発光強度が高い理由は、ネオジム
イオンの吸光、発光の波長域にわたって、大きな吸光お
よび発光のない三価を取りうる金属イオンを有するテト
ラ燐酸塩を母体として、これに発光中心となるネオジム
イオンを賦活したことによるものと思われる。また、Ｌ
ｉ，ＮａまたはＫなどのアルカリ金属の添加により発光
材料の結晶性が改善され、この結晶性の改善により発光
強度が更に向上されるものと思われる。The light emitting material of the present invention is basically composed of 4f of Nd.
Although it emits light by the 4f-4f transition of electrons, the reason why the emission intensity is higher than that of the conventional light emitting material is that absorption of neodymium ions, large absorption and trivalence without emission can be taken over the wavelength range of emission. It is considered that this is due to the fact that the tetraphosphate having metal ions was used as the base material and neodymium ions, which became the emission center, were activated. Also, L
It is considered that the addition of an alkali metal such as i, Na or K improves the crystallinity of the light emitting material, and this improvement in crystallinity further improves the emission intensity.
【００１０】本発明の赤外発光材料は、大きな発光出力
が得られるので、光学的マーキング用発光材料として好
ましい特性を備えている。前記母体を形成する三価のイ
オンとなる元素の種類によって異なるが、特に０．１≦
ｘ≦０．７の範囲の発光材料は大きな発光強度が得られ
る。Since the infrared light emitting material of the present invention can obtain a large light emission output, it has preferable characteristics as a light emitting material for optical marking. Depending on the kind of the element that becomes the trivalent ion forming the matrix, 0.1 ≦
A large light emission intensity can be obtained with a light emitting material in the range of x ≦ 0.7.
【００１１】前記のように、本発明では、三価を取りう
るイオンの濃度ｘを規定したが、この範囲外では十分満
足しうる発光強度は得られない。この理由は明らかでな
いが、例えば、ｘが０．０５未満では濃度消光により量
子効率が低下し、また、ｘが０．８超では発光中心であ
るネオジムイオンの濃度が希薄となるため十分な発光が
得られなくなるためであろうと想像される。As described above, in the present invention, the concentration x of ions capable of assuming trivalence is defined, but if the concentration is out of this range, sufficient emission intensity cannot be obtained. Although the reason for this is not clear, for example, when x is less than 0.05, the quantum efficiency is reduced due to concentration quenching, and when x is more than 0.8, the concentration of neodymium ions, which is the emission center, becomes dilute, so that sufficient emission is achieved. It is imagined that this is because it will not be obtained.
【００１２】本発明の発光材料は様々な方法で製造でき
るが、例えば、Ｎｄ2 Ｏ3 ，Ｇｄ2Ｏ3 ，Ｙ2 Ｏ3 また
は焼成により容易に酸化物に変化する炭酸化物、硝酸化
物、シュウ酸化物など、およびＬｉ2 ＣＯ3 ，ＮＨ4 Ｈ
2 ＰＯ4 を、Ｐが化学量論的組成よりも１．５倍以上、
Ｌｉが化学量論的組成よりも１．２倍以上過剰となるよ
うに秤量し、十分混合した後、アルミナ製の蓋付坩堝に
充填し、大気中で５００〜１０００℃、好ましくは６０
０℃〜９００℃で約０．５時間〜２０時間程度にわたっ
て焼成すればよい。その他、水熱合成法などによっても
得られるであろう。また、副次的ではあるが、本発明に
よる発光材料は坩堝から取り出す際、水に浸すだけで粉
体として得ることが出来るので、従来の発光材料（例え
ば、ＬｉＮｄＰ4 Ｏ12）とは異なり熱水による煮沸が不
要である。The luminescent material of the present invention can be produced by various methods. For example, Nd 2 O 3 , Gd 2 O 3 , Y 2 O 3 or carbonates, nitric oxides, and sulphurs which easily change into oxides by firing. Oxides, etc., and Li 2 CO 3 , NH 4 H
2 PO 4 , P is 1.5 times more than stoichiometric composition,
Li was weighed so as to be 1.2 times or more in excess of the stoichiometric composition, sufficiently mixed, and then filled in a crucible with a lid made of alumina, and 500 to 1000 ° C., preferably 60 in the atmosphere.
The firing may be performed at 0 ° C. to 900 ° C. for about 0.5 hours to 20 hours. In addition, it may be obtained by a hydrothermal synthesis method. Further, there is a secondary, but when the light emitting material according to the invention is taken out from the crucible, since only immersion in water can be obtained as a powder, conventional light emitting materials (e.g., LiNdP 4 O 12) different from the heat No boiling with water is required.
【００１３】図１は、下記の一般式、 ＬｉＧｄx Ｎｄ1-x Ｐ4 Ｏ12 (1) ＬｉＹx Ｎｄ1-x Ｐ4 Ｏ12 (2) ＬｉＧｄx Ｙx Ｎｄ1-2xＰ4 Ｏ12 (3) で示される発光材料中の三価をとる全てのイオン中のネ
オジムイオンの濃度と１０５０ｎｍにおける発光強度の
相対値との関係を示す特性図である。図示されているよ
うに、母体を形成する三価のイオンとしてＧｄ3+，Ｙ3+
を用いると、Ｎｄ3+イオンが高濃度のとき、Ｎｄ3+イオ
ンが発光材料中にある三価のイオンの全量であるときよ
りも発光は低下している。恐らくは、このとき同時に発
光材料の結晶性が変化しているために、濃度消光による
量子効率の低下が増大して発光が低下したものと考えら
れる。しかし、Ｎｄ3+イオンの濃度の減少に伴い、発光
強度は増加する。その理由として、例えば、濃度消光に
よる量子効率の低下が減少した結果、大きな発光が得ら
れたものと考えられる。更に、Ｎｄ3+イオン濃度が減少
すると、再び発光強度は低下する。この理由は、恐ら
く、発光中心であるＮｄ 3+イオンの濃度が減少した結果
であろう。そして、Ｇｄ3+またはＹ3+イオンの何れか一
方のみを、発光材料の母体として三価をとりうるイオン
として用いた場合、Ｎｄ3+イオンの濃度が０．７近辺の
とき最も強い発光が得られ、また、Ｇｄ3+およびＹ3+イ
オンを等量混合した場合は、Ｇｄ3+およびＹ3+イオンが
共に０．２である、つまり、Ｎｄ3+イオンが０．６近辺
のとき最も強い発光強度が得られることが判明した。従
って、前記(1) の一般式、ＬｉＧｄx Ｎｄ1-x Ｐ4 Ｏ12
で示される組成の発光材料の場合、好ましいｘの範囲
は、０．１≦ｘ≦０．６、最も好ましくは、０．２≦ｘ
≦０．５であり、前記(2) の一般式、ＬｉＹx Ｎｄ1-x
Ｐ4 Ｏ12で示される組成の発光材料の場合、好ましいｘ
の範囲は、０．２≦ｘ≦０．６、最も好ましくは、０．
２５≦ｘ≦０．５であり、前記(3) の一般式、ＬｉＧｄ
x Ｙx Ｎｄ1-2xＰ4 Ｏ12で示される組成の発光材料の場
合、好ましいｘの範囲は、０．２≦ｘ≦０．６、最も好
ましくは、０．３≦ｘ≦０．５である。FIG. 1 shows the following general formula: LiGdx Nd1-x PFour O12 (1) LiYx Nd1-x PFour O12 (2) LiGdx Yx Nd1-2xPFour O12 The ions in all trivalent ions in the luminescent material shown in (3)
Of the concentration of odymium ions and the emission intensity at 1050 nm
It is a characteristic view which shows the relationship with a relative value. Is shown
Gd as a trivalent ion forming the mother3+, Y3+
Is used, Nd3+When the concentration of ions is high, Nd3+Io
Is the total amount of trivalent ions in the luminescent material.
The light emission is decreasing. Probably at this time
Due to the change in crystallinity of the optical material,
It is thought that the decrease in quantum efficiency increased and the emission decreased.
Be done. But Nd3+Light emission with decreasing ion concentration
Strength increases. The reason is that, for example,
As a result of the decrease in quantum efficiency due to
It is thought to have been Furthermore, Nd3+Ion concentration decreases
Then, the emission intensity again decreases. The reason for this is probably
Nd, which is the emission center 3+Result of reduced ion concentration
Will. And Gd3+Or Y3+One of the ionic
Only one of them is an ion that can take trivalent as the matrix of the light emitting material.
When used as Nd3+Ion concentration around 0.7
When the strongest light emission is obtained and Gd3+And Y3+I
When mixing equal amounts of ON, Gd3+And Y3+Ion
Both are 0.2, that is, Nd3+Ions around 0.6
It was found that the strongest luminescence intensity was obtained at. Servant
Thus, the general formula of (1) above, LiGdx Nd1-x PFour O12
In the case of a light emitting material having a composition shown by
Is 0.1 ≦ x ≦ 0.6, most preferably 0.2 ≦ x
≦ 0.5, the general formula of (2) above, LiYx Nd1-x
PFour O12In the case of a light emitting material having a composition shown by
The range is 0.2 ≦ x ≦ 0.6, most preferably 0.
25 ≦ x ≦ 0.5, the general formula (3) above, LiGd
x Yx Nd1-2xPFour O12In the case of a luminescent material having the composition shown by
In this case, the preferable range of x is 0.2 ≦ x ≦ 0.6, and the most preferable range is
It is preferable that 0.3 ≦ x ≦ 0.5.
【００１４】図２は、一般式、ＬｉＧｄx Ｙy Ｎｄ
1-x-y Ｐ4 Ｏ12（但し、ｘ＋ｙ＝０．３である）で示さ
れる発光材料中のＧｄ3+イオンおよびＹ3+イオンの濃度
と１０５０ｎｍにおける発光強度の相対値の関係を示す
特性図である。この特性図から明らかなように、複数の
三価をとるイオンで母体を形成したときも、従来の発光
材料（例えば、ＬｉＮｄＰ4 Ｏ12）に比べて強い発光が
得られる。一般的に、式、ＬｉＧｄx Ｙy Ｎｄ1-x-y Ｐ
4 Ｏ12で示される組成の発光材料の場合、０．１≦ｘ＋
ｙ≦０．８、好ましくは、０．２≦ｘ＋ｙ≦０．６、最
も好ましくは、０．３≦ｘ＋ｙ≦０．５であり、かつ、
０．００１≦ｙ／（ｘ＋ｙ）≦０．９９９、好ましく
は、０．１≦ｙ／（ｘ＋ｙ）≦０．９、最も好ましく
は、０．３≦ｙ／（ｘ＋ｙ）≦０．７である。FIG. 2 shows the general formula LiGd x Y y Nd.
A characteristic diagram showing the relationship between the concentration of Gd 3+ ions and Y 3+ ions in the light-emitting material represented by 1-xy P 4 O 12 (where x + y = 0.3) and the relative value of the emission intensity at 1050 nm. Is. As is clear from this characteristic diagram, even when the matrix is formed with a plurality of trivalent ions, stronger light emission is obtained as compared with the conventional light emitting material (for example, LiNdP 4 O 12 ). In general, the formula LiGd x Y y Nd 1-xy P
In the case of a light emitting material having a composition represented by 4 O 12 , 0.1 ≦ x +
y ≦ 0.8, preferably 0.2 ≦ x + y ≦ 0.6, most preferably 0.3 ≦ x + y ≦ 0.5, and
0.001 ≦ y / (x + y) ≦ 0.999, preferably 0.1 ≦ y / (x + y) ≦ 0.9, and most preferably 0.3 ≦ y / (x + y) ≦ 0.7. .
【００１５】[0015]
【実施例】以下、実施例により本発明の発光材料の製造
および特性を例証する。EXAMPLES Hereinafter, the production and characteristics of the light emitting material of the present invention will be illustrated by examples.
【００１６】実施例１ Ｎｄ2 Ｏ3 ４．６３ｇ，Ｇｄ2 Ｏ3 １．５３ｇ，Ｌｉ2
ＣＯ3 ２．３３ｇおよびＮＨ4 Ｈ2 ＰＯ4 ２８．９９ｇ
からなる粉末原料を十分に混合し、アルミナ製の蓋付坩
堝に充填した後、電気炉に入れ、室温から４００℃まで
一定昇温速度で２時間、４００℃から７００℃まで一定
昇温速度で１時間昇温し、しかる後、７００℃で２時間
焼成した。焼成終了後、直ちに電気炉から取り出して空
気中で放冷させた。その後、坩堝中に注水し、１Ｎ硝酸
で洗浄し、次いで水洗し、最後に乾燥させて目的の発光
材料を得た。得られた発光材料の組成はＬｉＧｄ0.3 Ｎ
ｄ0.7 Ｐ4 Ｏ12であり、その平均粒径は６μｍであっ
た。 Example 1 Nd 2 O 3 4.63 g, Gd 2 O 3 1.53 g, Li 2
2.33 g CO 3 and 28.99 g NH 4 H 2 PO 4
After thoroughly mixing the powdered raw material consisting of, and filling the crucible with a lid made of alumina into an electric furnace, the temperature is raised from room temperature to 400 ° C at a constant heating rate for 2 hours, and from 400 ° C to 700 ° C at a constant heating rate. The temperature was raised for 1 hour, and then, firing was performed at 700 ° C. for 2 hours. Immediately after the firing was completed, it was taken out of the electric furnace and allowed to cool in the air. Then, water was poured into the crucible, washed with 1N nitric acid, then washed with water, and finally dried to obtain a desired light emitting material. The composition of the obtained light emitting material is LiGd 0.3 N
d 0.7 P 4 O 12 , and the average particle size was 6 μm.
【００１７】実施例２ Ｎｄ2 Ｏ3 ４．６３ｇ，Ｙ2 Ｏ3 １．４２ｇ，Ｌｉ2 Ｃ
Ｏ3 ２．３３ｇおよびＮＨ4 Ｈ2 ＰＯ4 ２８．９９ｇか
らなる粉末原料を十分に混合し、アルミナ製の蓋付坩堝
に充填した後、電気炉に入れ、室温から４００℃まで一
定昇温速度で２時間、４００℃から７００℃まで一定昇
温速度で１時間昇温し、しかる後、７００℃で２時間焼
成した。焼成終了後、直ちに電気炉から取り出して空気
中で放冷させた。その後、坩堝中に注水し、１Ｎ硝酸で
洗浄し、次いで水洗し、最後に乾燥させて目的の発光材
料を得た。得られた発光材料の組成はＬｉＹ0.3 Ｎｄ
0.7Ｐ4 Ｏ12であり、その平均粒径は６μｍであった。 Example 2 4.63 g of Nd 2 O 3 , 1.42 g of Y 2 O 3 and Li 2 C
A powder raw material consisting of 2.33 g of O 3 and 28.99 g of NH 4 H 2 PO 4 was thoroughly mixed and charged into an alumina crucible with a lid, which was then placed in an electric furnace and heated at a constant rate from room temperature to 400 ° C. The temperature was raised from 400 ° C. to 700 ° C. for 1 hour at a constant heating rate for 2 hours, and thereafter, firing was performed at 700 ° C. for 2 hours. Immediately after the firing was completed, it was taken out of the electric furnace and allowed to cool in the air. Then, water was poured into the crucible, washed with 1N nitric acid, then washed with water, and finally dried to obtain a desired light emitting material. The composition of the obtained light emitting material is LiY 0.3 Nd.
It was 0.7 P 4 O 12 , and its average particle size was 6 μm.
【００１８】実施例３ Ｎｄ2 Ｏ3 ４．２４ｇ，Ｇｄ2 Ｏ3 １．５２ｇ，Ｙ2 Ｏ
3 ０．９５ｇ，Ｌｉ2ＣＯ3 ２．３３ｇおよびＮＨ4 Ｈ2
ＰＯ4 ２８．９９ｇからなる粉末原料を十分に混合
し、アルミナ製の蓋付坩堝に充填した後、電気炉に入
れ、室温から４００℃まで一定昇温速度で２時間、４０
０℃から７００℃まで一定昇温速度で１時間昇温し、し
かる後、７００℃で２時間焼成した。焼成終了後、直ち
に電気炉から取り出して空気中で放冷させた。その後、
坩堝中に注水し、１Ｎ硝酸で洗浄し、次いで水洗し、最
後に乾燥させて目的の発光材料を得た。得られた発光材
料の組成はＬｉＧｄ0.2 Ｙ0.2 Ｎｄ0.6 Ｐ4 Ｏ12であ
り、その平均粒径は６μｍであった。 Example 3 Nd 2 O 3 4.24 g, Gd 2 O 3 1.52 g, Y 2 O
3 0.95 g, Li 2 CO 3 2.33 g and NH 4 H 2
A powder raw material consisting of 28.99 g of PO 4 was thoroughly mixed and charged into an alumina crucible with a lid, which was then placed in an electric furnace and heated from room temperature to 400 ° C. at a constant temperature rising rate for 2 hours, 40
The temperature was raised from 0 ° C. to 700 ° C. at a constant heating rate for 1 hour, and then calcined at 700 ° C. for 2 hours. Immediately after the firing was completed, it was taken out of the electric furnace and allowed to cool in the air. afterwards,
Water was poured into the crucible, washed with 1N nitric acid, washed with water, and finally dried to obtain a desired light emitting material. The composition of the obtained light emitting material was LiGd 0.2 Y 0.2 Nd 0.6 P 4 O 12 , and the average particle size was 6 μm.
【００１９】比較例 Ｎｄ2 Ｏ3 ７．０６ｇ，Ｌｉ2 ＣＯ3 ２．３３ｇおよび
ＮＨ4 Ｈ2 ＰＯ4 ２８．９９ｇからなる粉末原料を十分
に混合し、アルミナ製の蓋付坩堝に充填した後、電気炉
に入れ、室温から４００℃まで一定昇温速度で２時間、
４００℃から７００℃まで一定昇温速度で１時間昇温
し、しかる後、７００℃で２時間焼成した。焼成終了
後、直ちに電気炉から取り出して空気中で放冷させた。
その後、坩堝中に注水し、１Ｎ硝酸で洗浄し、次いで水
洗し、最後に乾燥させて目的の発光材料を得た。得られ
た発光材料の組成はＬｉＮｄＰ4 Ｏ12であり、その平均
粒径は６μｍであった。 Comparative Example A powder raw material consisting of 7.06 g of Nd 2 O 3 , 2.33 g of Li 2 CO 3 and 28.99 g of NH 4 H 2 PO 4 was thoroughly mixed and charged into an alumina crucible with a lid. , Put in an electric furnace, and from room temperature to 400 ℃ at a constant temperature rising rate for 2 hours
The temperature was raised from 400 ° C. to 700 ° C. at a constant heating rate for 1 hour, and thereafter, firing was performed at 700 ° C. for 2 hours. Immediately after the firing was completed, it was taken out of the electric furnace and allowed to cool in the air.
Then, water was poured into the crucible, washed with 1N nitric acid, then washed with water, and finally dried to obtain a desired light emitting material. The composition of the obtained light emitting material was LiNdP 4 O 12 , and the average particle size was 6 μm.
【００２０】前記の実施例１〜３および比較例で作製さ
れた発光材料を水溶性バインダ樹脂であるポリビニルピ
ロリドンに等重量混合分散し、これを白色樹脂板上に均
一に塗布してテストサンプルを作成した。このサンプル
に発光ダイオード光源から８１０ｎｍの光線を照射して
発光させ、その光をシリコン光受光素子で受光させ、受
光素子の出力を測定した。結果を図３に示す。図３で
は、比較例で得られた発光材料からなるサンプルのシリ
コン光受光素子の出力を１００とした。図３から明らか
なように、実施例で得られた各発光材料は何れも比較例
の発光材料よりも高い発光出力を示す。特に、実施例１
の発光材料の出力は１４０に達し、最も高かった。The light emitting materials prepared in Examples 1 to 3 and Comparative Example were mixed and dispersed in an equal weight with polyvinylpyrrolidone which is a water-soluble binder resin, and this was uniformly coated on a white resin plate to give a test sample. Created. This sample was irradiated with a light beam of 810 nm from a light emitting diode light source to emit light, and the light was received by a silicon light receiving element, and the output of the light receiving element was measured. The results are shown in Fig. 3. In FIG. 3, the output of the silicon light receiving element of the sample made of the light emitting material obtained in the comparative example is set to 100. As is clear from FIG. 3, each of the light emitting materials obtained in the examples shows higher light emission output than the light emitting materials of the comparative examples. In particular, Example 1
The output of the luminescent material reached 140, which was the highest.
【００２１】[0021]
【発明の効果】以上説明したように、本発明の発光材料
は、従来から光学的マーキング用発光材料として用いら
れてきたＬｉＮｄＰ4 Ｏ12よりも遥かに高い発光出力を
示すので、カードリーダなどで用いる光学的マーキング
用発光材料として特に優れている。As described above, the light emitting material of the present invention exhibits a much higher light emission output than LiNdP 4 O 12, which has been conventionally used as a light emitting material for optical marking. It is particularly excellent as a light emitting material for optical marking used.
【図１】ＬｉＧｄx Ｎｄ1-x Ｐ4 Ｏ12，ＬｉＹx Ｎｄ
1-x Ｐ4 Ｏ12およびＬｉＧｄx Ｙx Ｎｄ1-2xＰ4 Ｏ12で
示される発光材料の１０５０ｎｍにおける発光強度の相
対値を示す特性図である。FIG. 1 LiGd x Nd 1-x P 4 O 12 , LiY x Nd
Is a characteristic diagram showing relative values of emission intensity at 1050nm of the luminescent material represented by 1-x P 4 O 12 and LiGd x Y x Nd 1-2x P 4 O 12.
【図２】ＬｉＧｄx Ｙy Ｎｄ1-x-y Ｐ4 Ｏ12（但し、ｘ
＋ｙ＝０．３である）で示される発光材料の１０５０ｎ
ｍにおける発光強度の相対値を示す特性図である。FIG. 2: LiGd x Y y Nd 1-xy P 4 O 12 (where x
+ Y = 0.3) of the light-emitting material represented by 1050n
It is a characteristic view which shows the relative value of the light emission intensity in m.
【図３】実施例１〜３および比較例で得られた各発光材
料の発光出力を示す特性図である。FIG. 3 is a characteristic diagram showing the light emission output of each light emitting material obtained in Examples 1 to 3 and Comparative Example.
Claims (4)
れる少なくとも一種類以上のアルカリ金属元素であり、
ＢはＳｂ，Ｌｕ，Ｇａ，Ｓｃ，Ｙ，Ｌａ，Ｃｅ，Ｇｄ，
Ｉｎ，Ｂｉ，ＡｌおよびＴｌからなる群から選択される
少なくとも一種類以上の三価のイオンとなりうる金属元
素であり、０．０５≦ｘ≦０．８である）で示される組
成を有することを特徴とする赤外発光材料。1. The following general formula: AB x Nd 1-x P 4 O 12 (wherein A is at least one or more alkali metal elements selected from the group consisting of Li, Na and K,
B is Sb, Lu, Ga, Sc, Y, La, Ce, Gd,
A metal element capable of forming at least one kind of trivalent ion selected from the group consisting of In, Bi, Al and Tl, and having a composition represented by 0.05 ≦ x ≦ 0.8). Infrared light emitting material.
12（但し、０．１≦ｘ≦０．６である）で示される組成
を有する請求項１の赤外発光材料。2. The general formula LiGd x Nd 1-x P 4 O.
The infrared light emitting material according to claim 1, having a composition represented by 12 (provided that 0.1 ≦ x ≦ 0.6).
し、０．２≦ｘ≦０．６である）で示される組成を有す
る請求項１の赤外発光材料。3. The infrared light emitting material according to claim 1, having a composition represented by the general formula: LiY x Nd 1-x P 4 O 12 (where 0.2 ≦ x ≦ 0.6).
Ｏ12（但し、０．１≦ｘ＋ｙ≦０．８であり、かつ、
０．００１≦ｙ／（ｘ＋ｙ）≦０．９９９である）で示
される組成を有する請求項１の赤外発光材料。4. The general formula LiGd x Y y Nd 1-xy P 4
O 12 (however, 0.1 ≦ x + y ≦ 0.8, and
The infrared light emitting material according to claim 1, having a composition represented by 0.001 ≦ y / (x + y) ≦ 0.999.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5254897A JPH0782553A (en) | 1993-09-17 | 1993-09-17 | Infrared luminescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5254897A JPH0782553A (en) | 1993-09-17 | 1993-09-17 | Infrared luminescent material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0782553A true JPH0782553A (en) | 1995-03-28 |
Family
ID=17271368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5254897A Withdrawn JPH0782553A (en) | 1993-09-17 | 1993-09-17 | Infrared luminescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0782553A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008248052A (en) * | 2007-03-30 | 2008-10-16 | National Institute Of Advanced Industrial & Technology | Stress-induced light-emitting material for emitting ultraviolet ray, its manufacturing method, and its utilization |
| CN104403669A (en) * | 2014-11-08 | 2015-03-11 | 广东省工业技术研究院(广州有色金属研究院) | Phosphate fluorescent material suitable for electron beam excitation |
-
1993
- 1993-09-17 JP JP5254897A patent/JPH0782553A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008248052A (en) * | 2007-03-30 | 2008-10-16 | National Institute Of Advanced Industrial & Technology | Stress-induced light-emitting material for emitting ultraviolet ray, its manufacturing method, and its utilization |
| WO2008126466A1 (en) * | 2007-03-30 | 2008-10-23 | National Institute Of Advanced Industrial Science And Technology | Stress-luminescent material emitting ultraviolet, process for producing the same, and use thereof |
| CN104403669A (en) * | 2014-11-08 | 2015-03-11 | 广东省工业技术研究院(广州有色金属研究院) | Phosphate fluorescent material suitable for electron beam excitation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20020194494A1 (en) | Article authentication | |
| Song et al. | RGB tricolor and multimodal dynamic optical information encryption and decoding for anti-counterfeiting applications | |
| CN104981532A (en) | NItride Phosphor And Method For Manufacturing Same | |
| JP2005518475A (en) | Anti-Stokes fluorescent material composition | |
| WO2006104081A1 (en) | Infra-red light emitting fluorescent substance | |
| US5220166A (en) | Information reading method | |
| Xie et al. | Synthesis and photoluminescence properties of novel orange-emitting Sm3+-activated LaTiSbO6 phosphors for WLEDs | |
| CN112342021A (en) | Near-infrared broadband emission luminescent material, preparation method thereof and luminescent device comprising material | |
| Dogan et al. | Comparative studies on thermoluminescence characteristics of non-doped Mg2SiO4 prepared via a solid-state reaction technique and wet-chemical method: An unusual heating rate dependence | |
| CN110511754A (en) | A kind of tantalic acid alkali photostimulated phosphor and preparation method thereof | |
| JPH0782553A (en) | Infrared luminescent material | |
| CN110590162B (en) | Nanocrystalline transparent glass ceramic for multidimensional optical storage and preparation method thereof | |
| CN109111912A (en) | A kind of preparation of high power white LED nano-cluster core-shell fluorescent powder | |
| JP3336572B2 (en) | Infrared fluorescent substance and method for producing the same | |
| Ozawa et al. | Luminescence of Pr+ 3 Activated Y 2 O 2 S | |
| US6139774A (en) | Fluorescent substance | |
| RU2610767C2 (en) | INFRARED LUMINOPHOR OF COMPLEX ACTION BASED ON YTTRIUM ORTHOPHOSPHATE, ACTIVATED WITH IONS OF Yb3+ AND Er3+ | |
| JP3702354B2 (en) | Infrared phosphor | |
| JP3418746B2 (en) | ink ribbon | |
| JP3438188B2 (en) | Infrared light emitting phosphor | |
| JPH10298550A (en) | Infrared light-emitting fluorescent material | |
| US3487025A (en) | Rare earth tellurate phosphors | |
| CN114479856B (en) | Luminescent material, preparation method and application thereof | |
| CN113528131B (en) | Rare earth element doped zinc aluminosilicate complex phase light excitation luminescent material and preparation method thereof | |
| WO2024225460A1 (en) | Infrared persistently luminescent oxysulfide phosphor and luminescent composition for determining authenticity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20001128 |