LUMINESCENT BARIUM-HEXA-ALUMINATE, LUMINESCENT SCREEN PROVIDED WITH SUCH AN ALUMINATE AND LOW-PRESSURE MERCURY VAPOUR DISCHARGE LAMP PROVIDED WITH SUCH A SCREEN

Abstract: Luminescent Eu²⁺ activated barium-hexa-aluminate mainly having the crystal structure of β′-alumina and being defined by the formula (x-p)BaO.pEuO.(6-0.67x)Al₂O₃ in which 0.90≦x≦1.22 and 0.005≦p≦0.25 and in which 1 to 20 mol% of the BaO is replaced by at least one of the oxides CaO and 0.67Li₂O.

Description: The invention relates to a luminescent Eu²⁺ activated barium-hexa-aluminate mainly comprising the crystal structure of β′-alumina. The invention also relates to a luminescent screen provided with such an aluminate and to a low-pressure mercury vapour discharge lamp provided with such a screen. Eu²⁺ activated aluminates of Ba and/or Sr and/or Ca defined by the formula Ba x Sr y Ca z Eu p Al₁₂O₁₉ in which x + y + z + p = 1 and 0.001 ≦ p ≦ 0.1 are known from British Patent Specification 1,190,520 (PHN 2878). The said Patent Specification does not state any details on the crystal structure of these efficiently luminescent materials. It was, however, known that these materials have a hexagonal crystal structure which was assumed to relate to the structure of the mineral magnetoplumbite (BaFe₁₂O₁₉). This has indeed proved to be the case for both strontium-hexa-aluminate and for calcium-hexa-aluminate defined by the above-mentioned formula. However, the Article in Mat. Res. Bull., Vol. 21, pp. 1305-1310, 1986, proves that barium-hexa-aluminate occurs in two different phases, namely a barium-poor phase with the crystal structure of β-alumina and a barium-rich phase with the crystal structure of β′-alumina. The structure of the said two alumina phases is hexagonal and, although it is related to that of magnetoplumbite, it is clearly different therefrom and from each other. The Article further shows that these barium-hexa-aluminates luminesce efficiently upon activation by Eu²⁺ under excitation by short-wave ultraviolet radiation (for example 254 nm). The β-alumina phase then exhibits a blue-green emission in a band with a maximum at approximately 476 nm and a half value width of approximately 135 nm, whilst the β′-alumina phase emits blue radiation in a band with a maximum at approximately 437 nm and a half value width of approximately 55 nm. According to the said Article the two phases in which barium-hexa-aluminate occurs can be described with molecule formulas which are derived from β-alumina and β′-alumina, respectively. By replacing 75% of the Na⁺-ions by Ba²⁺-ions and the remaining 25% by O²-ions in the formula NaAl₁₁O₁₇ of β-alumina and in the formula Na 1.5 Al 10.5 O 16.5 of β′-alumina, Ba 0.75 Al₁₁O 17.25 for the barium-poor phase with the β-alumina structure is obtained and Ba 1.125 Al 10.5 O 16.875 for the barium-rich phase with β′-alumina structure is obtained. In these formulas the sum of the number of large ions (Ba²⁺ + O²⁻ and Na⁺ + O²⁻, respectively) per molecule is equal to 18. The comparatively narrow band emission with a maximum at 437 nm of Eu²⁺ activated barium-hexa-aluminate having the β′-alumina structure is very desirable for several practical applications. However, a drawback of this material is that disturbing quantities of the barium-poor phase with the β-alumina structure is obtained in addition to the desired barium-rich phase with the β′-alumina structure during preparation. Even in the case of starting from the stoichiometric quantities associated with the β′-alumina phase it appears that disturbing side phases may occur. A result thereof is that the barium-hexa-aluminate yields a considerable part of its emission at wavelengths of more than 500 nm. Consequently the material is less suitable in practice, for example for use as the blue component in a low pressure mercury vapour discharge lamp provided with luminescent materials which emit in the three narrow spectral ranges (the so-called three-line lamps). The object of the invention is to provide a luminescent Eu²⁺ activated barium-hexa-aluminate which mainly has the crystal structure of β′-alumina and whose emission above 500 nm is considerably suppressed. According to the invention a luminescent Eu²⁺ activated barium-hexa-aluminate mainly having the crystal structure of β′-alumina is characterized in that the aluminate is defined by the formula (x-p)BaO · pEuO · (6-0.67x)Al₂O₃ in which 0.90 ≦ x ≦ 1.22 and 0.005 ≦ p ≦ 0.25 and in which 1 to 20 mol% of the BaO is replaced by at least one of the oxides CaO and 0.67 Li₂O. Measurements have proved that the emission above 500 nm is considerably reduced in the Eu²⁺ activated barium-hexa-aluminates mainly having the crystal structure of β′-alumina, if the aluminate lattice comprises at least one of the elements Ca and Li. An explanation for this fact may be that the elements Ca and Li suppress the emission of the barium-hexa-aluminate having the crystal structure of β-alumina which is possibly present in a slight quantity. A second possible explanation is that the formation of the barium-hexa-aluminate having the crystal structure of β-alumina is suppressed by the elements Ca and Li during the preparation of the luminescent aluminate. The molecule formula of the barium-hexa-aluminate according to the invention is represented in an oxide form. The fundamental lattice xBaO · (6-0.67x)Al₂O₃, in which the sum of the large ions Ba²⁺ + O²⁻ is equal to 18 corresponds for x = 1.125 to the formula Ba 1.125 Al 10.5 O 16.875 mentioned in the opening paragraph. It has been found that the β′-alumina phase is obtained for values of x in the range of 0.90 ≦ x ≦ 1.22. The use according to the invention of the elements Ca and/or Li is represented in this case as a replacement of the oxide BaO by the oxides CaO and/or 0.67 Li₂O in which the sum of the number of large ions remains constant (namely 18). If more than 20 mol% of the BaO, that is to say, the BaO together with the BaO replaced by EuO is replaced by at least one of the oxides CaO and 0.67 Li₂O in the aluminate lattice, too large quantities of unwanted side phases are produced such as hexagonal calcium aluminate (CaAl₁₂O₁₉) having the crystal structure of magnetoplumbite and lithium aluminate (LiAl₅O₈) having the spinel structure. Due to the presence of such side phases the Eu²⁺ emission of the barium-hexa-aluminate having the crystal structure of β′-alumina is influenced detrimentally. If in the aluminate lattice less than 1 mol% of the BaO is replaced by CaO and/or 0.67 Li₂O, the concentration of Ca and/or Li is too low to achieve the envisaged favourable effect. As is common practice, the Eu concentration in the luminescent aluminates according to the invention may be chosen within a wide range. The above-mentioned concentrations are used for obtaining an efficient emission. This means that per mol of the aluminate 0.005 to 0.25 mol of BaO is replaced by EuO. Aluminates according to the invention which are characterized in that 1.05 ≦ x ≦ 1.20 and in that 5 to 15 mol% of the BaO is replaced by CaO and/or 0.67 Li₂O are preferred. The best results have been obtained with such concentrations of Ca and/or Li. Embodiments of luminescent Eu²⁺ activated barium-hexa-aluminates according to the invention will now be described in greater detail with reference to the accompanying drawing and a number of examples of preparation. In the drawing Figure 1 shows a low-pressure mercury vapour discharge lamp provided with a luminescent screen comprising a luminescent Eu²⁺ activated barium-hexa-aluminate according to the invention, and Figure 2 shows the spectral energy distribution of the emission of Eu²⁺ activated barium-hexa-aluminate according to the invention and of an Eu²⁺ activated barium-hexa-aluminate having the crystal structure of β′-alumina which comprises none of the oxides of Ca and/or Li. The radiation energy E is plotted in arbitrary units as a function of the wavelength λ in this Figure. Figure 1 shows in a diagrammatic cross-section a low-pressure mercury vapour discharge lamp having a tubular glass wall 1. Electrodes 2 and 3 between which the discharge is maintained during operation are placed at the ends of the lamp. The lamp contains a small quantity of mercury and a rare gas as a starter gas. The wall 1 constitutes a luminescent screen and serves as a support for the luminescent layer 4 comprising a luminescent aluminate according to the invention. The layer 4 may be provided in a conventional manner on the wall 1, for example by means of a suspension comprising the luminescent material. Example 1. A mixture was made of 3.424 of BaCO₃ 0.161 of CaCO₃ 9.176 of Al₂O₃ 0.176 of Eu₂O₃ 0.049 of H₃BO₃. This mixture was fired three times for 1 hour in a weakly reducing atmosphere (N₂ comprising 5 vol.% of H₂) at a temperature of 1550°C.After each firing treatment the product was cooled and pulverised. The aluminate thus obtained in which 8 mol% of the BaO is replaced by CaO is defined by the formula 1.009 BaO · 0.093 CaO · 0.058 EuO · 5.225 Al₂O₃. The emission spectrum of this aluminate upon excitation by 254 nm radiation is shown by the solid-line curve 1 in Figure 2. For the purpose of comparison the broken-line curve 2 shows the emission spectrum of the barium-hexa-aluminate 0.981 BaO · 0.109 EuO · 5.273 Al₂O₃ comprising none of the oxides CaO and/or 0.67 Li₂O. This Figure 2 shows that the emission above 500 nm in the aluminate comprising Ca according to the invention is considerably suppressed as compared with the known aluminate. Examples 2 to 15. In a corresponding manner as described in Example 1 a number of aluminates according to the invention was obtained with the fundamental lattice defined by the formula 1.102 BaO · 0.058 EuO · 5.225 Al₂O₃ in which CaO and/or 0.67 Li₂O was substituted in different quantities for BaO. Unless otherwise stated, the 0.67 Li₂O was added to the firing mixture as Li₂CO₃. Table 1 below states the quantum efficiency Q (in %) upon excitation by 254 nm radiation of these materials and also of the material according to Example 1. The Table also states the UV absorption A (in %) and the wavelength λ max (in nm) at which the emission is maximum. E₁₂₋₈₈ (in nm) indicates the width of the uninterrupted wavelength range in which 76% of the energy is emitted. Outside this range the remaining 24% of the emission is found, namely 12% at smaller wavelengths and 12% at larger wavelengths. As the value of E₁₂₋₈₈ is smaller, the quantity of energy which is emitted above 500 nm is smaller. Furthermore Table 1 indicates by means of a and b (in mol%) the quantity of BaO which is replaced by CaO and 0.67 Li₂O, respectively. If a flux is used in the preparation of the barium-hexa-aluminate this flux is mentioned in Table 1. For the purpose of comparison the barium-hexa-aluminate comprising none of the oxides CaO and/or 0.67 Li₂O mentioned in Example 1 is incorporated in the Table. This aluminate is indicated by BAL. By mixing an aluminate according to the invention with a green luminescing (Ce, Tb)MgAl₁₁O₁₉ and a red luminescing Y₂O₃: Eu³⁺ a mixture is obtained which is very suitable for use in a so-called three-line lamp. Table 2 below compares such a three-line mixture with a similar mixture in which barium-hexa-aluminate without Ca and/or Li substitution is used at different colour temperatures of the emitted radiation. The Table states the relative luminous flux ETA (in Lm/W) of the mixtures at different colour temperatures (in K). The mixtures with the aluminate according to the invention in which Ca is present are indicated in the table by BAL-Ca, whilst the mixture with the aluminate without Ca and/or Li substitution are indicated by BAL. A three-line mixture with (Ce, Tb)MgAl₁₁O₁₉ and Y₂O₃: Eu³⁺ was made of the aluminate 0.983 BaO · 0.066 CaO · 0.055 EuO · 5.262 Al₂O₃. Of this mixture low-pressure mercury vapour discharge lamps of the TLD 36W type were made with an initial colour point x = 0.3832 and y = 0.3762 and with a colour temperature of approximately 3850 K. Table 3 below shows the relative luminous flux (in Lm/W), the relative luminous flux with respect to that at 100 operating hours (in %) and the colour point shift Δx/Δy with respect to the initial colour point of these lamps after 0, 100, 350 and 1000 operating hours.

Claims: 1. A luminescent Eu²⁺ activated barium-hexa-aluminate mainly having the crystal structure of β′-alumina, characterized in that the aluminate is defined by the formula (x-p)BaO · pEuO · (6-0.67x)Al₂O₃ in which 0.90 ≦ x ≦ 1.22 and 0.005 ≦ p ≦ 0.25 and in which 1 to 20 mol% of the BaO is replaced by at least one of the oxides CaO and 0.67 Li₂O. 2. A luminescent aluminate as claimed in Claim 1, characterized in that 1.05 ≦ x ≦ 1.20 and in that 5 to 15 mol% of the BaO is replaced by CaO and/or 0.67 Li₂O. 3. A luminescent screen having a luminescent layer provided on a support, comprising a luminescent aluminate as claimed in any one of Claims 1 and 2. 4. A low-pressure mercury vapour discharge lamp provided with a luminescent screen as claimed in Claim 3.

Inventors: VERLIJSDONK, JOHANNUS GODEFRIDUS
Applicants: N.V. PHILIPS' GLOEILAMPENFABRIEKEN
Application year: 1988
Main classification: C09K11
IPC codes: C09K11, H01J61