CN1206734A - Luminous silicate-borate substance - Google Patents

Luminous silicate-borate substance Download PDF

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CN1206734A
CN1206734A CN98115943A CN98115943A CN1206734A CN 1206734 A CN1206734 A CN 1206734A CN 98115943 A CN98115943 A CN 98115943A CN 98115943 A CN98115943 A CN 98115943A CN 1206734 A CN1206734 A CN 1206734A
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silicate
borate
luminous
borate substance
luminous silicate
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CN1105765C (en
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W·图斯
G·罗思
I·菲思克
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates
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Abstract

The invention relates to a plurality of activated luminescent silicate-borate compounds, which has improved luminescent properties compared with the conventional luminescence material, and has excellent stability in the impact of ultraviolet short wave radiation, so the activated luminescent silicate-borate compounds is suitable for fluorescent screen, especially low pressure vapor mercury lamp. The luminescence material of the invention is based on metaborate of rare earth metal and has a formula of: (Y,La)(1-x-y-z)Ce(x)Gd(y)Tb(z)(Mg,Zn,Cd)(1-p)Mn(p)B(5-q-s)(Al,Ga)(q)X(s)O(10), which could be used for emitting layer of fluorescent screen and low pressure vapor mercury lamp.

Description

Luminous silicate-borate substance
The present invention relates to the luminescent silicate-borate substance after the various activation, its luminosity has improvement than traditional luminophore, and under UV shortwave irradiation, remarkable stability is arranged, so they preferably are applicable to fluorescent screen, are particularly useful for the low-voltage mercury arc lamp of all types and design.
Because the maximum wavelength of their typical terbium emissions is at about 541-543nm, the narrow compound of those emission bands preferably is used as the screen component in the luminescent lamp, especially for compact fluorescent lamp and three phosphorus pipe luminescent lamps.These compounds comprise following luminophore: according to the cerium-zirconium aluminic of AT351635: Tb (CAT), according to DE3326921 and US4,891,550 lanthanum orthophosphate: Ce, Tb (LAP) and according to the phosphoric acid lanthanum silicate of DE3248809: Ce, Tb (LAPS) and according to the Y of EP037688 2SiO 5: Ce, Tb, they are its most important materials.All these luminophores are characteristics with its thermostability height and luminous efficiency height all.But, be its shortcoming owing to preparation requires temperature to make the production cost height at 1300-1600 ℃.
Also having a kind of is five boric acid gadolinium magnesium at the maximum luminophore of 542nm emission: Ce, Tb, describe in EP023068 to some extent.The feature of luminophore CBT is that the production temperature is relatively low, only is slightly higher than 1000 ℃.Because its stability is high and emissivity is good, is used for luminophore CAT, LAP, LAPS and Y 2SiO 5: Ce, Tb are of equal value, but its shortcoming to be the particle of most of fluorescence borate substance more coarse relatively, irregular and be difficult to processing.
The object of the invention is to develop a kind of luminophore, and its emissivity and processing characteristics are further improved, and can be used for standard fluorescent lamp, miniature energy-saving lamp and modern luminescent lamp.
For reaching this purpose, adopted luminophore based on the rare earth metal metaborate of following general formula according to the present invention:
(Y, La) 1-x-y-zCe xGd yTb z(Mg, Zn, Cd) 1-pMn pB 5-q-s(Al, Ga) q(X) sO 10Wherein X is Si; Ge; P; Zr; V; Nb; Ta; W，y＝z＝p＝0 0．01 ≤x≤ 1．0 0 ≤q≤ 1．0 0＜s≤ 1．0z＝p＝0y≠0 0．01 ≤x≤ 1-y 0．02 ≤y≤ 0．80 0 ≤q≤ 1．0 0＜s≤ 1．0p＝0z≠0 0．01 ≤x≤ 1-y-z 0 ≤y≤ 0．98 y＋z ≤ 0．99 0．01 ≤z≤ 0．75 0 ≤q≤ 1．0 0＜s≤ 1．0z＝0p≠0 0．01 ≤x≤ 1-y 0 ≤y≤ 0．99 0．01 ≤p≤ 0．30 0 ≤q≤ 1．0 0＜s≤ 1．0p≠0z≠0 0．01 ≤x＜1-y-z 0 ≤y≤ 0．98 0．01 ≤z≤ 0．75 x＋z ≤ 0．99 0．01 ≤p≤ 0．30 0 ≤q≤ 1．0 0＜s≤ 1．0。
According to B.Saubat, M.Vlasse and the C.Fouassier article on solid state chemistry magazine 34 (1980) 3,271-277 pages or leaves, the complete provable space group P2 that has of these luminophors 1The monoclinic structure of/c, can with LnMgB 5O 10Quite.
According to luminophore of the present invention, emission maximum is arranged and/or wide emission band is arranged at 630nm at 542nm.Quantity and the type of peaked drift of emission band and added element X are closely related.
With reference to following each embodiment test-results, will more at large be illustrated the present invention.
List in again among table 1-table 5 and Fig. 1-Fig. 3 according to the test-results of luminophore of the present invention and each embodiment.
In table 1-table 4, " Rel.int. " is illustrated in the relative emissive porwer at emission maximum place, and " Rel.integr. " expression is the accumulation emissive porwer relatively, " q " expression relative quantum yield.The nothing of luminophore replace sample (X=0) be used as with Welker at fluorescence magazine 48/49 (1991), 53 pages and the Smets data in 16 (1987) 292 pages of chemistry and physics materials (Mater.Chem.and Phys.) are carried out the quantum yield comparative standard.
Embodiment is:
1). the luminophore according to table 2 embodiment 2 has general formula:
Gd 0．6Ce 0．2Tb 0．2MgAl 0．1Si 0．05B 4．85O 10，
Parent material is:
H 3BO 3??5．176g
CeO 2?????0．431g
Gd 2O 3??1．360g
MgCO 3(1.230g 0.05 molar excess)
SiO 2?????0．038g
Tb 4O 7??0．467g
Al 2O 3??0．064g
The preparation: with oxidized form or comprise that the parent material that can be converted into oxide compound mixes with the magnesium of 0.05 molar excess and according to the excessive boric acid between 5-50% of reaction conditions according to aforementioned ratio, again in 600 ℃ down at the beginning of calcination 30 minutes, after intermediate product is ground, powder further is heated to 1035 ℃ in corundum crucible, calcination under the reductive condition of nitrogen/hydrogen mixture and under this temperature of reaction 3 hours.Wash the gained final product with water, again dried and screened in addition.The gained compound has emission maximum at the 542nm place, as shown in Figure 1.
2). the luminophore according to table 2 embodiment 5 has general formula:
Gd 0．6Ce 0．2Tb 0．2MgAl 0．1Si 0．05B 4．80O 10，
Initial substance is:
H 3BO 3??5．176g
CeO 2?????0．431g
Gd 2O 3??1．360g
MgCO 3(1.230g 0.05 molar excess)
SiO 2?????0．075g
Tb 4O 3??0．467g
Al 2O 3??0．064g
Preparation: this preparation is according to the carrying out that is analogous to embodiment 2 in the table 1.The luminophor of gained has emission maximum at the 542nm place.
3). the luminophore according to table 2 embodiment 9 has general formula:
Gd 0．8Ce 0．2Mg 0．9Mn 0．1Al 0．1Si 0．05B 4．85O 10，
Initial substance is:
H 3BO 3??12．748g
CeO 2?????1．291g
Gd 2O 3??5．439g
MgCO 3(3.342g 0.05 molar excess)
MnCO 3????0．4311g
Al 2O 3??0．1911g
SiO 2?????0．113g
Preparation: this parent material is mixed fully, be introduced in the stove under the room temperature, in nitrogen atmosphere, be heated to 560 ℃ again.Keep taking out intermediate product afterwards in 30 minutes, ground.Again this intermediate product through fine grinding is sent in the stove, in reductive condition and 1015 ℃ of following calcinations 4 hours.After being cooled to 500 ℃ again, with the final product of this grain of 80 ℃ of water agitator treatings, and then in addition dry.The product that obtains thus has peaked emission band at the 628nm place.The puberty spectrogram is shown in Fig. 2.
4). the luminophore according to embodiment in the table 2 11 has general formula:
Gd 0．8Ce 0．2Mg 0．9Mn 0．1Si 0．1B 4．9O 10，
Initial substance is:
H 3BO 3??12．748g
CeO 2?????1．291g
Gd 2O 3??5．439g
MgCO 3(3.342g 0.05 molar excess)
MnCO 3????0．431g
SiO 2?????0．226g
Preparation: with all parent materials all by handling in table 2 embodiment 9 methods, but calcination 6 hours under described temperature of reaction.The luminophor that forms has peaked emission band at the 629nm place.
5). the luminophore according to embodiment in the table 3 14 has general formula:
Gd 0．6Ce 0．2Tb 0．2Mg 0．9Mn 0．1Al 0．1Si 0．05B 4．85O 10，
Initial substance is:
H 3BO 3??4．801g
CeO 2?????0．431g
Gd 2O 3??1．360g
MgCO 3(1.113g 0.05 molar excess)
MnCO 3????0．144g
SiO 2?????0．075g
Tb 4O 3????0．467g
Al 2O 3????0．064g
Preparation: this parent material is heated to 580 ℃ in nitrogen atmosphere, after keeping 30 minutes, from stove, takes out, ground.Then with the further calcination 2 hours under 1025 ℃ of reductive conditions of this intermediate product.After taking out and grinding, under same condition, carry out the calcination second time.Product after cooling and the washing has the feature line of departure of terbium and the emission band of manganese is arranged at the 628nm place at the 542nm place, as shown in Figure 3.
Table 1
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
????1 ????Gd 0.6Ce 0.2Tb 0.2MgAl 0.1B 4.9O 10 Heat is washed ????100 ????100 ?0.93
????2 ????Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Si 0.05B 4.85O 10 Heat is washed ????103 ????102 ?0.95
????3 ????Gd 0.6Ce 0.2Tb 0.2MgAl 0.05Si 0.05B 4.9O 10 EDTA ????101 ????100 ?0.94
????4 ????Gd 0.6Ce 0.2Tb 0.2MgSi 0.1B 4.9O 10 EDTA ????99 ????99 ?0.91
????5 ????Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Si 0.1B 4.8O 10 Heat is washed ????101 ????100 ?0.93
????6 ????Gd 0.6Ce 0.2Tb 0.2ZnAl 0.05Si 0.05B 4.9O 10 Be untreated ????102 ????101 ?0.94
????7 ????Gd 0.6Ce 0.2Tb 0.2Mg 0.75Cd 0.25A1 0.1Si 0.05B 4.85O 10 Be untreated ????102 ????101 ?0.94
Table 2
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
8 Gd 0．8Ge 0．2Mg 0．9Mn 0．1Al 0．1B 4．9O 10 Heat is washed 100 100 0．90
9 Gd 0．8Ge 0．2Mg 0．9Mn 0．1Al 0．1Si 0．05B 4．85O 10 Heat is washed 104 105 0．94
10 Gd 0．8Ge 0．2Mg 0．9Mn 0．1Al 0．05Si 0．05B 4．9O 10 Be untreated 102 104 0．93
11 Gd 0．8Ge 0．2Mg 0．9Mn 0．1Si 0．1B 4．9O 10 EDTA 99 101 0．91
12 Gd 0．8Ge 0．2Mg 0．9Mn 0．1Al 0．25Si 0．75B 4．9O 10 Heat is washed 100 101 0．91
Table 3
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
13 Gd 0．6Ge 0．2Td 0．2Mg 0．9Mn 0．1Al 0．1B 4．9O 10 Heat is washed 100 100 0．90
14 Gd 0．6Ge 0．2Td 0 ．2Mg 0．9Mn 0．1Al 0．1Si 0．05B 4．85O 10 Heat is washed 102 103 0．92
15 Gd 0．6Ge 0．2Td 0．2Mg 0．9Mn 0．1Si 0．1B 4．9O 10 Heat is washed 99 100 0．90
Table 4
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
?16 ????Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Ge 0.05B 4.85O 10 Heat is washed ????101 ????101 ?0.91
?17 ????Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Zr 0.05B 4.85O 10 Heat is washed ????100 ????100 ?0.9
?18 ????Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1P 0.05B 4.85O 10 Heat is washed ????102 ????101 ?0.91
?19 ????Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1V 0.05B 4.85O 10 Heat is washed ????99 ????99 ?0.89
?20 ????Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Nb 0.05B 4.85O 10 Heat is washed ????95 ????94 ?0.84
?21 ????Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1Ta 0.05B 4.85O 10 Heat is washed ????96 ????96 ?0.85
Owing to be used to prepare the excessive of required boric acid and two valency positively charged ions are excessive, in the neutralization of table 1-table 4 in the above-described embodiments,, therefore, simply be written as O to because the charge compensation that Sauerstoffatom caused that substituent produced of selection does not give consideration 10To replace O 10+s
According to table 1 couple luminophore BSCT, according to table 2 couple luminophore BSCM, according to table 3 couple luminophore BSCTM, all prove with result according to table 4 couple luminophore BSCX, they have surpassed the characteristics of luminescence of known so far simple pentaborate luminophore significantly in some cases, particularly by mixing silicon in addition and forming based on the example of only using magnesium activatory silicate-borate luminophore according to table 5, its structure obviously is different from the structure of known simple pentaborate so far, contraction has generally all taken place in lattice, increases as the θ value size as shown in the diffractometer image.
In table 5, the Si=0 of embodiment 8 represents CBM, and Si=0.05 represents BSCM among the embodiment 10, among the embodiment 11 Si=0.1 represent BSCM and in addition in embodiment 9 Si=0.05 represent BCSM.In the embodiment that all have been studied, similar structural changes all takes place, the central ion size reduces to have caused the lattice contraction, but size increases and then causes lattice dilatation.For first kind of situation, mainly observe the characteristics of luminescence and improve; For second kind of situation, compare with the luminous pentaborate of routine, but do not observe variation, or slightly destroy.
Embodiment shown in the table 1-5 all shows, not only particularly silicate-borate but also germanic acid borate and borophosphoric acid hydrochlorate all have outstanding basic lattice because of activating with cerium, terbium, gadolinium and magnesium, and, can be used for fluorescent screen individually or as mixture because they have the extraordinary characteristics of luminescence.Particularly, they can be used for as the luminescent layer at low-voltage mercury arc lamp, and then cause several percentage points of optical throughput gains.Table 5
????A ????B ????C ????D ????E ?B-C ?B-D ?B-E
?Si=0 ?Si=0.05 Si=0.05 in addition Si=0.1
CBM embodiment 8 BSCM embodiment 10 BSCM embodiment 9 BSCM embodiment 11
????hkl ????Θ ????Θ ????Θ ????Θ ????ΔΘ ????ΔΘ ????ΔΘ
????100 ????13.5 ????13.52 ????13.52 ????13.54 ????-0.02 ????-0.02 ????-0.04
????10-2 ????14.24 ????14.24 ????14.24 ????14.26 ????0 ????0 ????-0.02
????11-1 ????15.48 ????15.46 ????15.5 ????15.54 ????0.02 ????-0.02 ????-0.06
????11-2 ????18.42 ????18.42 ????18.44 ????18.44 ????0 ????-0.02 ????-0.02
????002 ????18.84 ????18.86 ????18.88 ????18.9 ????-0.02 ????-0.04 ????-0.06
????20-2 ????20.5 ????20.52 ????20.5 ????20.5 ????-0.02 ????0 ????0
????020 ????23.34 ????23.36 ????23.36 ????23.4 ????-0.02 ????-0.02 ????-0.06
????21-1 ????23.64 ????23.64 ????23.66 ????23.68 ????0 ????-0.02 ????-0.04
????021 ????25.24 ????25.22 ????25.24 ????25.26 ????0.02 ????0 ????-0.02
????12-1 ????25.56 ????25.58 ????25.56 ????25.58 ????-0.02 ????0 ????-0.02
????21-3 ????25.92 ????25.92 ????25.94 ????25.92 ????0 ????-0.02 ????0
????120 ????27.1 ????27.1 ????27.1 ????27.12 ????0 ????0 ????-0.02
????12-2 ????27.48 ????27.48 ????27.48 ????27.5 ????0 ????0 ????-0.02
????102 ????29.78 ????29.8 ????29.78 ????29.84 ????-0.02 ????0 ????-0.06
????022 ????30.2 ????30.22 ????30.22 ????20.24 ????-0.02 ????-0.02 ????-0.04
????10-4 ????30.86 ????30.86 ????30.86 ????30.88 ????0 ????0 ????-0.02
????21-4 ????31.14 ????31.14 ????31.14 ????31.16 ????0 ????0 ????-0.02
????121 ????31.64 ????31.64 ????31.64 ????31.68 ????0 ????0 ????-0.04
????30-2 ????31.98 ????32 ????32.02 ????32.06 ????-0.02 ????-0.04 ????-0.08
????12-3 ????32.3 ????32.32 ????32.32 ????32.32 ????-0.02 ????-0.02 ????-0.02
????22-3 ????33.1 ????33.1 ????33.08 ????33.1 ????0 ????0.02 ????0
????31-2 ????34.12 ????34.14 ????34.16 ????34.16 ????-0.02 ????-0.04 ????-0.04
????31-4 ????35.04 ????35.08 ????35.1 ????35.08 ????-0.04 ????-0.06 ????-0.04
????220 ????36.22 ????36.22 ????36.22 ????36.26 ????0 ????0 ????-0.04
????211 ????36.46 ????36.48 ????36.48 ????36.5 ????-0.02 ????-0.02 ????-0.04
????023 ????37.16 ????37.18 ????37.18 ????37.2 ????-0.02 ????-0.02 ????-0.04
????31-1 ????37.6 ????37.62 ????37.66 ????37.68 ????-0.02 ????-0.06 ????-0.08
Average drift ????-0.010 ????-0.016 ????-0.035

Claims (9)

1. luminous silicate-borate substance, it is based on the metaboric acid rare earth metal salt, and its general formula is:
(Y, La) 1-x-y-zCe xGd yTb z(Mg, Zn, Cd) 1-pMn pB 5-q-s(Al, Ga) q(X) sO 10Wherein X is Si; Ge; P; Zr; V; Nb; Ta; W，y＝z＝p＝0 0．01 ≤x≤ 1．0 0 ≤q≤ 1．0 0＜s≤ 1．0z＝p＝0y≠0 0．01 ≤x≤ 1-y 0．02 ≤y≤ 0．80 0 ≤q≤ 1．0 0＜s≤ 1．0p＝0z≠0 0．01 ≤x≤ 1-y-z 0 ≤y≤ 0．98 y＋z ≤ 0．99 0．01 ≤z≤ 0．75 0 ≤q≤ 1．0 0＜s≤ 1．0z＝0p≠0 0．01 ≤x≤ 1-y 0 ≤y≤ 0．99 0．01 ≤p≤ 0．30 0 ≤q≤ 1．0 0＜s≤ 1．0p≠0z≠0 0．01 ≤x＜1-y-z 0 ≤y≤ 0．98 0．01 ≤z≤ 0．75 x＋z ≤ 0．99 0．01 ≤p≤ 0．30 0 ≤q≤ 1．0 0＜s≤ 1．0。
2. according to the luminous silicate-borate substance described in the claim 1, wherein y=z=p=0 and 0.01≤x≤0.50.
3. according to the luminous silicate-borate substance described in the claim 1, wherein z=p=0 and 0.01≤x≤0.50 and 0.05≤y≤0.75 and x+y≤1.
4. according to the luminous silicate-borate substance described in the claim 1, wherein p=0 and 0.01≤z≤0.75 and x+y+z=1.
5. according to the luminous silicate-borate substance described in the claim 1, wherein z=0 and 0.01≤p≤0.30 and x+y=1.
6. according to the luminous silicate-borate substance described in the claim 1, wherein 0.01≤p≤0.30 and 0.01≤z≤0.75 and x+y+z=1.
7. according to each described luminous silicate-borate substance among the claim 1-6, wherein these luminophores a kind of or several are used for fluorescent screen as mixture.
8. according to each described luminous silicate-borate substance among the claim 1-6, wherein these luminophores a kind of or several are used for the luminescent layer of fluorescent layer or low-voltage mercury arc lamp as mixture.
9. according to each described luminous silicate-borate substance in claim 1-6 and 8, it is to be arranged on the discharge vessel inboard of its diameter greater than the low-pressure steam mercuryarc lamp of 5mm, and the Radiant UV Power of discharge is greater than 200W/m 2
CN98115943A 1997-07-12 1998-07-10 Luminous silicate-borate substance Expired - Fee Related CN1105765C (en)

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DE19730005A DE19730005C2 (en) 1997-07-12 1997-07-12 Silicate borate phosphors
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CN106905967B (en) * 2017-02-20 2019-04-09 中国计量大学 A kind of borophosphate green emitting phosphor and preparation method thereof
CN114538459A (en) * 2022-01-06 2022-05-27 上海电力大学 Preparation method of borate lithium ion battery cathode material and lithium ion battery
CN114538459B (en) * 2022-01-06 2024-05-10 上海电力大学 Preparation method of borate lithium ion battery anode material and lithium ion battery

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DE19730005A1 (en) 1999-01-14
KR100358573B1 (en) 2002-12-18
DE19730005C2 (en) 1999-11-25

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