Fast-moving infrared luminophor based on yttrium orthophosphate having xenotime structure

FIELD: chemistry.

SUBSTANCE: fast-moving infrared luminophor based on yttrium orthophosphate has the structure of natural xenotime mineral and has chemical composition with the following empirical formula: Y1-x-yNdxPryPO4 where 1∗10-2≤x≤5∗10-2; 5∗10-4≤y≤1∗10-2. When excited with radiation pulses in the 0.80-0.82 mcm range, the luminophor has Stokes infrared-band luminescence build up and attenuation time in the 1.03-1.1 mcm and 1.30-1.45 mcm regions of not more than 150 mcs.

EFFECT: improved properties of the luminophor.

3 dwg, 4 tbl, 12 ex

 

The invention relates to the chemical industry and can be used in the production of infrared phosphors comprehensive principle, with the excitation pulsed laser radiation range of 0.80-0,960 μm unique combination of hidden machine-readable spectral-kinetic properties:

- defined and reproducible position in the spectrum of luminescence of two groups of Stokes IR bands of luminescence in the spectral range of 1.03-1.1 and 1,30-1,45 m at the excitation radiation of the range of 0.80-of 0.82 microns;

- defined and reproducible nature of the dependence of the Stokes intensity of the IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm from the wavelength of the excitation radiation in the range of 0.80-0.96 μm;

- defined and reproducible nature of the curves rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30;

- of 1.45 μm after application and removal of the exciting pulse of the range of 0.80-of 0.82 microns;

- defined and reproducible time values rise and decay of the two groups of Stokes IR bands of luminescence in the areas of 1.03-1.1 and 1,30-1,45 μm within 60 to 150 μs.

Bystrolyetyascim infrared phosphor comprehensive principle-based yttrium orthophosphate has the structure of a natural mineral xenotime, and has a chemical composition, answer what s the following empirical formula:

Y1-x-yNdxPryPO4,

where 1·10-2≤x≤5·10-2; 5·10-4≤y≤1·10-2.

Bystrolyetyascim infrared phosphor-based yttrium orthophosphate is designed to create a hidden machine-readable fluorescent labels.

Known phosphor-based orthophosphate yttrium and rare earth elements (REE) (European patent EP No. 1108772 A2, CL SC 11/81 from 20.06.2001,), the chemical composition of which is described by the following chemical formula:

LnxCeyTbzPO4,

where Ln is La, Gd, Y and 0≤x≥1; 0≤y≥1; 0≤z≤0,4; x+y+z=1.

Main field of application is the manufacture of fluorescent lamps. Under UV excitation in fluorescent lamps specified phosphor emits in the yellow-orange region of the spectrum. The main disadvantages of this phosphor, excluding the possibility of its use as an IR phosphor, is that it does not absorb radiation in the range of 0.80-of 0.82 μm and not fluorescent in the area of 1.03-1.1 and 1,30-1,45 μm. These shortcomings are fundamentally physical in nature and due to the absence in the composition of the phosphor rare earth ions (RSI), as effectively absorb radiation from the field of 0,80-of 0.82 μm, and emitting in the region of 1.03-1.1 and 1,30-1,45 mm.

To improve lighting, operational and technological parameters of the above phosphor (LnxCe y, Tbz, PO4) proposed to enter into his composition of Pb and Sn (U.S. Pat. Japan No. 1-165689, CL C09K 11/81 from 29.06.1989 g), Hf and Zr (U.S. Pat. Japan No. 57-187383, CL SC 11/475 from 18.11.1982 g), Sb (U.S. Pat. Japan No. 62-089790, CL SC 11/81 from 24.04.1987,), Li, B, S (U.S. Pat. Japan No. 9249879, CL C09K 11/81 from 19.07.1991,), Tm, SiO2B2O3(U.S. Pat. Japan No. 3167289, CL C09K 11/08 from 19.07.1991 g), Dy, Al2O3, SiO2, LiF (U.S. Pat. Japan No. 63-154785, CL C09K 11/79 from 28.06.1988,), Li, Na, K, Rb, Cs, SiO2(U.S. Pat. U.S. No. 4629582, CL 252/301 .4 R from 16.12.1986 g), H3BO3(U.S. Pat. U.S. No. 4764301, CL 252/3014 R from 16.08.1988 year). These modified phosphors on the basis of REE orthophosphate have the same drawbacks, namely the lack of absorption of infrared radiation in the field of 0,80-of 0.82 μm and the effective Stokes IR luminescence in the area of 1.03-1.1 and 1,30-1,45 mm.

Known non stoichiometric ytterbium phosphate with a low infrared reflectivity (U.S. patent No. 5911921, CL 252/584 from 15.06.1999,). The proposed material is intended for use as an infrared component in invisible ink used for printing the information of bands such as the barcode. The advantage of this material is the high absorption of infrared radiation from the area of 0.90-0.98 μm. The main disadvantage is the lack of Stokes IR luminescence in the area of 1.03-1.1 and 1,30-1,45 m at the initiation of IR radiation 0,80-of 0.82 μm. This week is the STATCOM is also fundamental in nature and due to the fact, in the composition of the proposed material completely absent rare earth ions emitting in the field 1,30-1,45 mm.

Known phosphor-based orthophosphate yttrium and REE, activated by ions of trivalent praseodymium Pr3+(C.A.Hebbink et al. Lathanide (III) - Doped Nanoparticles That Emit in the Near - Infrared. Adv. Mat. 2002, v.14, No. 16, p.1146-1150; R.C.Popp. Phosphors based on rare-earth phosphates. I. Spectral properties of some rare - earth phosphates J. Electrochem. Soc. 1968, v.115, no. 6, p.841-846; R.C.Popp. Phosphors based on rare - earth phosphates. Fast decay phosphors. J. Electrochem. Soc. v.115, no. 6, p.531-535). These phosphors can be used in medical computer tomography, different types of fluorescent displays and as scintillators.

In the spectrum of the stationary luminescence of these phosphors under UV excitation observed several groups of bands of luminescence corresponding to optical transitions from excited States of the ion Pr3+listed in table 1.

Table 1
The observed groups of bands of luminescence and related optical transitions from excited States of the ion Pr3+listed in table 1
Band luminescence, mcmOptical transition
700-770 3P0→3F3/4
825-8301D2→3H6
870-8951D2→3F2
1000-10801D2→3F3/4
1260-13501G4→3H5
1450-15401D2→1G4

The main disadvantage of phosphors based on orthophosphate yttrium and REE ions-activated WG3+that excludes completely the possibility of their use as bystrolyetyascim infrared phosphor, is that they do not absorb the radiation range of 0.80-of 0.82 μm and for this reason, under these excitation conditions are not lumines cent. This disadvantage of the known phosphors on the basis of orthophosphate yttrium and REE ions-activated Pr3+that is the fundamental physical nature and due to the lack of ion Pr3+the absorption bands in the area 0,80-of 0.82 μm.

The closest in chemical composition, technical essence and the achieved result to the claimed invention is selected as a prototype LUMIN the Fort on the basis of yttrium orthophosphate, activated ions Nd3+which has the following chemical composition (Patent PRC No. 101525539 (A), CL SC 11/81 from 09.09.2009,):

Y1-xNdxPO4,

where 99≤1-x/x≤9 or 1·10-2≤x≤1·10-1.

The specified phosphor can be used in medical CT scanner, various types of displays, as well as for protection of securities. The analysis of spectral-kinetic properties of the proposed prototype of the phosphor based on yttrium orthophosphate activated by ions of Nd3+allowed us to establish the following:

1. In the absorption spectrum of the phosphor based on yttrium orthophosphate activated by ions of Nd3+in the area of 0.60-0.96 μm are observed absorption bands corresponding to optical transitions from the ground level4I9/2ion Nd3+listed in table 2.

Table 2
Absorption band, mcmOptical transition
0,600-0,6504I9/22H11/2
0,67-0,704I9/24F9/2
0,72-0,764I9/24F7/2, S3/2
0,78-0,834I9/24F5/2,2H9/2
0,83-0,914I9/24F3/2

The most intensive absorption band in the region 0,78-of 0.83 μm (transitions4I9/24F5/2,2H9/2). In the area of 0.94-0.98 µm proposed prototype of the phosphor based on yttrium orthophosphate activated by ions of Nd3+that does not absorb.

2. Range of stationary radiation proposed prototype infrared phosphor-based yttrium orthophosphate activated by ions of Nd3+when the excitation pulse radiation range of 0.80-0,82 contains in the area of 1.03-1.1 and 1,30-1,45 µm two groups Stokes IR luminescence bands (figure 1), corresponding to the following optical transitions from the excited level4F3/2ion Nd3+on the stark components of the States of4I11/2and4I13/2(figure 2).

Range of stationary luminescence known phosphor Y0,98Nd0,02PO4upon excitation by laser radiation 0,810 μm presented in figure 1.

The scheme of the possible optical transitions between ions Nd+3and Pr+in solid solutions of Y1-x-yNdxPryPO4when the excitation laser is the first radiation 0,810 µm are presented in figure 2.

3. The intensity of these IR bands of luminescence depends on the concentration of ions Nd3+in the phosphor-based yttrium orthophosphate (table 3). As shown in table 3 records the optimal composition of the proposed prototype of the phosphor based on yttrium orthophosphate activated by ions of Nd3+with impulse excitation radiation range of 0.80-of 0.82 μm maximum intensity of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm, corresponds to the following empirical formula Y0,98Nd0,02PO4.

4. The Stokes intensity of the IR bands of luminescence in the area of 1.03 and 1.1 and 1.3 to 1.45 μm is also dependent on the wavelength of the excitation pulse (table 3), which is associated with a different degree of absorption by the phosphor excitation radiation. The maximum intensity of the Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm is achieved when the excitation pulse radiation range of 0.80-of 0.82 μm, when the condition most complete absorption due to transitions4I9/2-4F5/2,2H9/2pulsed radiation range 0,8-of 0.82 μm (table 3). When the excitation pulse radiation of the range of 0.94-0.96 μm proposed prototype infrared phosphor optimal composition of Y0,98Nd0,02PO4not luminesce due to the lack of propagate in the field of 0.94-0.98 μm (table 3). This dependence of the intensity of the two bands of the IR bands of luminescence in the area of 1.03-1.1 and 1,35-1,45 μm from the wavelength of the excitation pulse can be used as a hidden protective luminescent characteristic, allowing reliable identification (Yes - no) valuable papers when two modes of excitation.

Table 3
According to the Stokes intensity of the IR bands of luminescence of the phosphor Y1-xNdxPO4from the concentration of ions Nd3+when the excitation pulse radiation 0,810 and 0,960 mcm
The concentration of the ions Nd3+xThe relative intensity of Stokes IR bands of the phosphors in the area of 1.03-1.1 µm, % upon excitationThe relative intensity of Stokes IR luminescence bands in the area 1,30-1,45 µm % upon excitation
λin=0,810 mcmλin=0,960 mcmλin=0,810 mcmλin=0,960 mcm
1·10-313,10 13,30
5·0-347,9046,90
7,5·10-369,4069,50
1·10-271,5072,10
1,5·10-290,20to 92.10
2·10-210001000
2,5·10-295,1095,50
3·10-283,30to 85.20
4·10-262,5061,70
5·10-246,5046,90

5. Proposed prototype of the phosphor based on yttrium orthophosphate activated by ions of Nd3+optimal composition of Y0,98Nd0,02PO4has at excitation pulse radiation range of 0.80-of 0.82 μm defined and reproducible nature of the curves rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 µm (figure 3). Time constants of rise and decay of the two groups of the IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm of this phosphor is 200 and 170 μs, respectively (table 4).

The decay curves of Stokes IR bands of luminescence in the field 1,30-1,45 microns proposed prototype phosphor Y0,98Nd0,02PO4(1) and the proposed technical solution (2) is presented in figure 3.

Comparative optical characteristics of the phosphors synthesized on the prototype and the claimed invention, are presented in table 4.

Thus, from the presented data it follows that the proposed prototype of the phosphor based on yttrium orthophosphate activated by ions of Nd3+optimal composition of Y0,98Nd0,02PO4has a number needed to create the and its basis bystrolyetyascim infrared phosphor practically important for the practical application of spectral-kinetic properties, namely:

- defined and reproducible position in the spectrum of luminescence of two groups of Stokes IR bands of luminescence in the spectral range of 1.03-1.1 and 1,30-1,45 m;

- defined and reproducible nature of the dependence of the Stokes intensity of the IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm from the wavelength of the excitation pulsed radiation range of 0.80-0.96 μm.

The main disadvantage of the proposed prototype of the phosphor based on yttrium orthophosphate activated by ions of Nd3+optimal composition of Y0,98Nd0,02PO4is inappropriate to modern requirements bystrolyetyascim infrared phosphors for high-speed processing of securities high values rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm, which are 200 and 170 μs, respectively (table 4). According to these requirements, the time of rise and decay of Stokes IR bands of infrared luminescence of phosphors designed for high-speed processing of securities should not exceed 150 μs.

The aim of the present invention is to create a new bystrolyetyascim infrared phosphor-based yttrium orthophosphate activated by ions of Nd3+with the excitation pulse emission is m the range of 0.80-of 0.82 μm time of rise and decay of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm is not more than 150 μs.

To achieve this goal in the first place it was necessary to reduce the known phosphor-based yttrium orthophosphate activated by ions of Nd3+time life level4F3/2which upon excitation by pulsed radiation range of 0.80-of 0.82 μm is highlighting two groups Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 µm (figure 1). Reducing the lifetime of the excited state of4F3/2ion Nd3+can be achieved due to the nonradiative transfer of electronic excitation energy from this level to close in energy metastable levels of the other rare-earth ion. In this regard, the idea arose to create a new bystrolyetyascim infrared phosphor by the introduction of the well-known phosphor-based yttrium orthophosphate activated by ions of Nd3+additionally another rare earth ion, providing for pulsed radiation range of 0.80-of 0.82 μm course of the above process nonradiative energy transfer. For the practical implementation of this idea, it was necessary to find RZ-ion having such properties. As follows from figure 2, such a rare earth ion may be an ion of Pr3+.

The technical result of the present invention is directed and reproducible decrease in BP is the times of rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 µm known phosphor-based yttrium orthophosphate, activated ions Nd3+when the excitation pulse radiation 0,80-of 0.82 μm.

This technical result is achieved by the fact that the well-known phosphor-based yttrium orthophosphate activated by ions of Nd3+, further comprises a trivalent praseodymium ions of Pr3+and has a chemical composition corresponding to the following empirical formula:

Y1-x-yNdxPryPO4,

where 1·10-2≤x≤5·10-2; 5·10-4≤y≤1·10-2.

According to regenerator analysis proposed bystrolyetyascim infrared phosphor has the structure of a natural mineral xenotime (space group I41amd, the local symmetry of the rare earth ion Ln3+-D2d).

In relation to the prototype of the claimed invention has the following distinctive features:

1. Declared bystrolyetyascim IR phosphor further comprises in the cation sublattice of yttrium orthophosphate ions of Pr3+.

2. The ferric ions of Pr3+in the inventive bystrolyetyascim IR phosphor varies: 5·10-4≤y≤1·10-2.

The essence of the claimed invention is that the technical result is achieved with the use of the totality of the distinguishing characteristics:

1. Introduction in the cationic sublattice know what these luminara based on yttrium orthophosphate, activated ions Nd3+addition of the necessary amount (5·10-4≤y≤1·10-2ions of Pr3+provides due to the proximity of the energies of the excited level4F3/2ion Nd3+and1G4ion Pr3+nonradiative energy transfer from ions of Nd3+ions of Pr3+with the generation of multiple phonons. In the course of the above process reduces the lifetime of the excited state of4F3/2and, as a consequence, reduction of time of rise and decay displayed with this level of two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm. Decontamination of the upper excited levels of G11/2,2To15/2,2G9/2ion Nd3+due to the nonradiative transfer of energy to the metastable levels3P1,3I6,3P0ion Pr3+(2) apparently, also helps to reduce the time of rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 mm.

2. The increase in the concentration of ions of Pr3+in these claims the concentration limits allows targeted and reproducible reduction of the time of rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm inthe widest ranging from 175 to 200 up to 60 to 150 μs.

Using the entire set of marked features allows you to get a new bystrolyetyascim infrared phosphor comprehensive principle-based yttrium orthophosphate with the structure of natural xenotime with the excitation pulsed laser radiation range of 0.80-0,960 μm unique combination of hidden machine-readable spectral-kinetic properties:

- defined and reproducible position in the spectrum of luminescence of two groups of Stokes IR bands of luminescence in the spectral range of 1.03-1.1 and 1,30-1,45 m at the excitation pulse radiation range of 0.80-of 0.82 microns;

- defined and reproducible nature of the dependence of the Stokes intensity of the IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm from the wavelength of the excitation pulsed radiation range of 0.80-0.96 μm;

- defined and reproducible nature of the curves rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30;

- of 1.45 μm after application and removal of the exciting pulse of the range of 0.80-of 0.82 microns;

- defined and reproducible values of time constants of rise and decay of the two groups of Stokes IR bands of luminescence in the areas of 1.03-1.1 and 1,30-1,45 μm within 60 to 150 μs.

Spectral-kinetic properties of the new bisociative infrared luminova is and are determined by the fundamental physical parameters of the matrix of the phosphor (space group I4 1amd, the local symmetry of the rare earth ion Ln3+-D2dand the energy structure of terms ion Nd3+and Pr3+(figure 2) and therefore have a defined and reproducible character.

Specified in the claims limits of ions of neodymium and praseodymium, included in the new bystrolyetyascim IR phosphor-based yttrium orthophosphate, determined experimentally based on the conditions of obtaining sufficient for practical purposes, the Stokes intensity of the IR bands of radiation in the area of 1.03-1.1 and 1,30-1,45 μm and minimum values of the time constants of rise and decay of these IR bands.

In this case a reduction of the content of neodymium ions to values smaller than those indicated in the claims, causes a reduction of the Stokes intensity of the IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 microns and increase the decay time of these IR bands. The decrease in the content of praseodymium to values smaller than those indicated in the claims, leads to an increase in the time of rise and decay of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm. The increase in the content of neodymium ions to a value greater than specified in the claims, leads to a significant decrease in the intensity of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm due concentrationg the fighting. The increase in the content of praseodymium ions to a value greater than specified in the claims, leads to a significant reduction in the intensity of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 mm.

Therefore, between the features and the technical result of the claimed invention has a causal relationship, because these signs only in aggregate achieve the desired technical result.

According to the authors ' knowledge, the set of essential features that characterize the essence of the claimed invention, is not known in what has been achieved to date technology that allows to make a conclusion about conformity of the invention, the criterion of "novelty", and the essence of the invention not obvious to experts from the achieved level of equipment, since it is not detected by the above-mentioned effect on the resulting technical result is a new property of an object is the totality of characteristics that differ from the prototype of the claimed invention, which allows to make a conclusion about its compliance with the criterion of "inventive step".

The set of essential features that characterize the invention, in principle, can be reused in the production of the IR phosphor-based orthophosphate yttrium and REE, activated ions Nd3+that allows to make a conclusion about conformity of the invention, the criterion of "industrial applicability".

Declare bystrolyetyascim IR phosphor using the entire set of distinctive features is described by the following examples:

Example 1 (Prototype).

22,14 g of yttrium oxide, 0,672 g of neodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. The resulting mixture was transferred into Lundby crucible covered with a lid and was progulivali in air at a temperature of 1250°C for two hours. After cooling, the obtained phosphor-based yttrium orthophosphate activated by ions of Nd3+, washed with distilled hot water to pH 6-7. The washed phosphor was dried at a temperature of 100-120°C and sieved through sieve No. 76. The chemical composition of the obtained phosphor corresponds to the following chemical formula: Y0,98Nd0,02PO4. Lighting parameters of the synthesized prototype phosphor are shown in table 4.

Example 2.

To prepare bystrolyetyascim IR phosphor according to the claimed invention 22,136 g of yttrium oxide, 0,672 oxide of neodymium, 0,0165 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate & rdquo; the tion was mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 3.

To prepare bystrolyetyascim IR phosphor according to the claimed invention 22,13 g of yttrium oxide, 0,672 oxide of neodymium, 0,0330 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 4.

To prepare bystrolyetyascim IR phosphor according to the claimed invention 22,03 g of yttrium oxide, 0,672 oxide of neodymium, 0,0165 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 5.

To prepare bystrolyetyascim IR Lumi is of three according to the claimed invention 21,92 g of yttrium oxide, 0,672 oxide of neodymium, 0,330 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 6.

To prepare bystrolyetyascim IR phosphor according to the claimed invention of 22.0 g of yttrium oxide, 0,840 oxide of neodymium, 0,0330 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 7.

To prepare bystrolyetyascim IR phosphor according to the claimed invention 21,97 g of yttrium oxide, 0,840 oxide of neodymium, 0.0825 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor were conducted according to Primero. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 8.

To prepare bystrolyetyascim IR phosphor according to the claimed invention 21,92 g of yttrium oxide, 0,840 oxide of neodymium, 0,165 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 9.

To prepare bystrolyetyascim IR phosphor according to the claimed invention 21.8 g of yttrium oxide, 0,840 g of neodymium oxide, 0,330 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 10.

To prepare bystrolyetyascim IR phosphor according to the claimed invention of 21.9 g of yttrium oxide, 1.01 g of neodymium oxide, 0,0330 g of praseodymium oxide,28,0 g ammonium phosphoric acid dogsleding (NH 4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 11.

To prepare bystrolyetyascim IR phosphor according to the claimed invention 21.8 g of yttrium oxide, 1.01 g of neodymium oxide, 0,165 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR phosphor are shown in table 4.

Example 12.

To prepare bystrolyetyascim IR phosphor according to the claimed invention of 21.7 g of yttrium oxide, 1.01 g of neodymium oxide, 0,330 g of praseodymium oxide, 28,0 g ammonium phosphoric acid dogsleding (NH4)2HPO4and 0.5 g of lithium carbonate were thoroughly mixed in a porcelain mortar. All other processing operations on the synthesis of this phosphor was performed according to example 1. Chemical composition and lighting parameters obtained bystrolyetyascim IR LUMIN the handicap given in table 4.

Note: the Relative intensity of Stokes IR luminescence was determined from the spectra of radiation. The excitation of the luminescence was carried out by radiation of a semiconductor laser L-940/50/30/ with output power of 50 mW and a wavelength of 942 nm, and L-810/50/30 with output power of 50 mW and a wavelength of 813 nm layer of powder on a metal substrate without binder (geometry 0-45°). Radiation spectra in the range 400-2000 nm was recorded using monochromator MDR-204. As the photodetector used photodetector FPU-FCS (PbS). The relative intensity of the phosphors according to the proposed technical solution was determined relative to the intensity of the prototype.
The kinetics of the rise and decay of luminescence in the emission band of the phosphor 1032 nm was recorded using monochromator MDR-204 and photodetecting unit FPU-1. Excitation was carried out by a semiconductor laser ATC-C1000-100AMF-940-5-F200 output power of 800 mW.
The time constant of decay was determined by the curve of decrease in the intensity (afterglow) to the level of 1/e relative activities is but the luminescence intensity at the moment of switching off the exciting pulse.

As shown in examples data (table 4), stated bystrolyetyascim infrared phosphor has compared to the proposed prototype of the phosphor based on yttrium orthophosphate activated by ions of Nd3+optimal composition of Y0,98Nd0,02PO4lower values of time constants of rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.01-1.1 and 1,30-1,45 mm.

Thus, successfully solved the problem of creating a new bystrolyetyascim infrared phosphor with a unique combination of spectral-kinetic parameters, namely:

- defined and reproducible position in the spectrum of luminescence of two groups of Stokes IR bands of luminescence in the spectral range of 1.03-1.1 and 1,30-1,45 m at the excitation pulse radiation range of 0.80-of 0.82 microns;

- defined and reproducible nature of the dependence of the Stokes intensity of the IR bands of luminescence in the area of 1.03-1.1 and 1,30-1,45 μm from the wavelength of the excitation pulsed radiation range of 0.80-0.96 μm;

- defined and reproducible nature of the curves rise and decay of the two groups of Stokes IR bands of luminescence in the area of 1.03-1.1 and 1,30;

- of 1.45 μm after application and removal of the exciting pulse of the range of 0.80-of 0.82 microns;

- defined and reproducible time values rise and decay of the two groups of Stokes IR bands of luminescence in the areas of 1.03-1.1 and 1,30-1,45 μm within 80-150 μs.

The application of the new bystrolyetyascim IR phosphor with such a complex spectral-kinetic properties will provide:

- increase the level of protection securities against tampering through the use of phosphor, is not known from modern technology;

- non-contact method of determining the authenticity of the securities;

high - speed sorting of securities on the counting and sorting machines, combined with control of their authenticity;

- expansion of the range of domestic IR phosphors used for the protection of the securities.

New bystrolyetyascim IR phosphor-based yttrium orthophosphate activated by ions of Nd3+and Pr3+took place in 2009-2010 several cycles experienced and pilot tests at the manufacturer's securities. According to the test results bystrolyetyascim IR phosphor conforms to the spectral-kinetic and printing-technological properties and is recommended for industrial production. To date, registered in the established order all necessary technical documentation (technical, technological regulations) and organized its industrial production.

Bystrolyetyascim infrared phosphor-based yttrium orthophosphate activated ions trehvalentnaya, characterized in that it additionally contains in the cation sublattice of yttrium orthophosphate trivalent praseodymium ions and has a chemical composition corresponding to the following empirical formula:
Y1-x-yNdxPryPO4,
where 1·10-2≤x≤5·10-2; 5·10-4≤y≤1·10-2.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: method involves mixing a tantalum compound with aqueous solution of a terbium salt in stoichiometric ratio which satisfies the composition of terbium tantalate, and thermal treatment of the obtained suspension. The tantalum compound used is tantalum hydroxide, and the terbium salt solution used is terbium acetate solution. The product undergoes thermal treatment at 850-900°C for 8-10 hours.

EFFECT: low synthesis temperature and duration of the process.

1 ex,1 tbl

FIELD: chemistry.

SUBSTANCE: polymer luminescent composition for obtaining white light excited by a blue light-emitting diode contains the following components, pts. wt: transparent polymer 100; photoluminescent phosphor based on garnet Y3Al5O12:Ce or Gd3Al5O12:Ce, or based on a mixture of said compounds 1.5-5.0; polyethylene wax in form of powder with particle size of 18-30 mcm 0.1-0.7; stabiliser 0.2-1.0. The transparent polymer used can be polycarbonate, polystyrene or a copolymer of styrene with acrylonitrile and butadiene. The stabiliser can be a compound from a group of sterically hindered phosphites.

EFFECT: Invention enables to obtain a protective lighting composition which provides low colour temperature, improved colour coordinates.

5 cl, 1 dwg, 2 tbl

FIELD: physics.

SUBSTANCE: in one version luminescent materials are in form of an aluminate, silicate, germanate or their combination and contain lead and/or copper as well as Eu and/or Mn, or Eu and Dy. In another version the luminescent materials are in form of a silicate or a combination of silicate and germanate and contain lead or copper, as well as Mn and/or Eu. In the third version the luminescent materials are in form of antimonite or a combination of antimonite and germanate and contain lead and/or copper, as well as Mn. The luminescent materials can be germanate or a combination of germanate and silicate and contain lead or copper, as well as Mn or Eu. In the last version the luminescent materials are in form of a phosphate or a combination of phosphate and silicate and contain lead or copper, as well as Mn and/or Eu.

EFFECT: disclosed luminescent materials enable to obtain colour rendering index in a light-emitting device Ra>90, colour temperature range from 2000 K to 8000 K and are characterised by better stability to effect of water, moisture and polar solvents.

7 cl, 20 tbl, 6 ex

FIELD: fire safety.

SUBSTANCE: luminescent composition for hidden marking, exposed when radiated with visible, infrared or ultraviolet radiation, contains binary mix, which includes luminophore with long afterglow on the basis of strontium aluminate, which is activated with europium, dysprosium and yttrium - LDP-1-3M, and photoluminophore with yellow, blue, red or white glow colour. Luminophores are taken with the mass ratio of 70:30. For even glow field, size of luminophore particles is selected in the range of 1-25 mcm, and flow glow of "Star sky" type - in the range of 20-180 mcm. Fire-prevention fireproofing composition includes fire-prevention composition and luminescent additive - specified binary mix. Method for marking of fire-prevention compositions consists in preparation of specified binary mixture, its introduction in amount of 0.01-35 wt parts per 100 wt parts of polymer binder. Produced marking is applied manually, by explication and printing methods in the form of information or graphic symbols, signs, text.

EFFECT: afterglow brightness and duration increase, as well as fire resistance, temperature range of afterglow expands, as a result, fast and reliable detection of fire-prevention composition is provided, as well as visualisation of extinguishing site.

3 cl, 4 tbl

The invention relates to materials for quantum electronics and can be used as active media low level solid-state lasers with optical pumping, in devices of computer science for information display

The invention relates to the technology of fluorescent materials on the basis of yttrium and europium and can be used for the manufacture of plastic film greenhouse

The invention relates to fluorescent compositions that can be used as a filler of plastic film for greenhouses and hothouses

FIELD: physics.

SUBSTANCE: described is novel assembling of semiconductor devices combined with optically active compositions. In particular, light-emitting semiconductors based on an InGaN structure, combined with highly efficient optically active langasite crystals La3Ga5SiO14. When activating the langasite, said composition interacts with radiation of the InGaN structure. The langasite absorbs high-energy photons emitted by the InGaN structure, and re-emits light with longer wavelength. Short-wave, high-energy radiation of the InGaN structure is mixed with longer wavelength radiation of the optically active composition and forms a wide spectrum which is perceived by a viewer as white light.

EFFECT: design of a wideband light source based on semiconductor structures, where a langasite photoluminescent phosphor with high radiation excitation efficiency, characteristic of InGaN light-emitting diodes, re-emits light in the middle range of the visible spectrum.

19 cl, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: disclosed is a luminescent composition for marking roads, which contains an aluminate type luminescent (phosphorescing) pigment and polymer binder selected from a group comprising: epoxy, urethane, acrylate, alkyd and composite polymer resins. The luminescent pigment is pre-treated in order to protect it from moisture using solutions of reagents selected from a group comprising mono-substituted phosphates, H2SO4, H3PO4, a mixture of tri- or disubstituted phosphates and at least one acid: HCl, H3SO4 or HNO3. Disclosed also is a luminescent paint for making roads, which contains an aluminate type luminescent (phosphorescing) pigment or a luminescent composition and a water or non-water based road paint or enamel. In another version, the luminescent paint is obtained by mixing a pigment which first protected from hydrolysis, polymer binder and a water or non-water based road paint or enamel: - luminescent pigment 2-60; polymer binder 4-20; road paint or enamel 94-20.

EFFECT: invention provides reliable protection of the pigment from hydrolysis, enables regulation of the amount of polymer binder which affects colour characteristics and technological aspects, as well as the size of particles of the luminescent pigment, which is important when mixing the pigment with components of compositions or paints.

4 cl, 8 tbl, 58 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a colourless phosphorescing luminophor, which is a coordination compound of terbium (III) with [2-(aminocarbonyl)phenoxy]acetic acid (HL2) and having formula Tb(L2)3, and specifically: , having high quantum efficiency of luminescence, considerable luminescence intensity and fluorescence maxima at 20500, 18300, 17000, 16000 cm-1.

EFFECT: possibility of use in protecting bond payer and documents from forgery, and as radiating substances in electroluminescent devices.

1 dwg, 1 ex

FIELD: physics.

SUBSTANCE: described is light-converting material containing a matrix and at least one composite which converts UV radiation to radiation of a different colour, with particle size from 10 nm to 1000 nm, selected from a group ZnO:Zn and rare-earth element compounds of formula: MexaAybRzc , where Me denotes a metal, selected from a group comprising yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, ytterbium, aluminium, bismuth, manganese, calcium, strontium, barium, zinc or mixture thereof; A denotes a metal selected from a group comprising cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, terbium, ytterbium, titanium, manganese; R is an element selected from a group comprising oxygen, sulphur, boron, titanium, aluminium and/or compounds thereof with each other; a, b and c denote the charge on the Me ion, A or R, respectively, x≥1, 1.0 ≥ y ≥ 0.0001, z is defined by ax + by = cz. The invention also describes a composition for producing said material, containing the following in wt %: said composite - 0.001-10.0; matrix-forming component - the rest.

EFFECT: invention increases intensity of converting UV radiation to infrared radiation, blue to green spectrum region, and therefore increases plant yield.

27 cl, 25 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in production of inorganic yttrium oxysulphide-based multifunctional anti-Stokes luminophors which can be used for converting infrared radiation to visible luminescence, for protecting bond paper and documents, strict accounting forms, conformity marks of goods and articles, excise and identification marks, banknotes, as well as for making emergency and signal light systems, evacuation, fire, warning and indicator light marks, for pointers in shafts, tunnels, overpasses, metro and passages for information-direction boards in motorways and decorative cosmetics. The yttrium oxysulphide-based luminophor is activated by titanium ions and coactivated by magnesium ions, and also contains a cationic sublattice of trivalent ytterbium and erbium ions and has a chemical composition corresponding to the following empirical formula: (Y1-X-YYbxEry)202S:Ti0.12,Mg0.04, where 0.01<X<0.05; 0.01<Y<0.05.

EFFECT: more intense visible anti-Stokes luminescence during excitation of infrared radiation in the 0,90-0,98 mcm range.

7 cl, 1 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention describes a method of modifying anti-Stokes luminophors based on oxychlorides of rare-earth elements, involving treatment of a luminophor with low-melting glass with flow temperature of 560-600°C in amount of 7-20% of the weight of the initial luminophor at 560-600°C for 0.5-1 hour.

EFFECT: obtaining modified anti-Stokes luminophor with high output and high moisture resistance with retention of high level of luminous intensity during infrared excitation.

9 ex

FIELD: physics, optics.

SUBSTANCE: invention relates to photoluminophors designed for converting emission of blue light-emitting diodes to the yellow-red region of the spectrum in order to obtain resultant white light, particularly to a cerium doped luminophor based on yttrium aluminium garnet used in two-component light-emitting diode light sources. The invention describes a luminophor for light sources which contain aluminium, yttrium, cerium, lutetium and oxygen in the following ratio: (Y1-xCex)3Al5O12 and 5-60 wt % over 100% (Lu1-yCey)2O3, where x=0.005-0.1; y=0.01-0.1. The invention provides a fine-grained luminophor with luminescent emission band maximum at λ≈590 nm, while lowering temperature and duration of synthesis.

EFFECT: use of such a luminophor in a two-component light source with a blue light-emitting diode enables to obtain resultant "warm" white light with high colour rendering index, increases uniformity of light scattering and reduces energy consumption during synthesis.

1 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: invention is meant for the chemical industry and can be used to protect bond paper and valuable documents, strict accounting forms, conformity marks of articles, excise and certification marks. An infrared luminophor having formula Y2-x-yErxCeyO2S, where x=0.20-0.45; 1·10-4≤y≤5·10-3 is described.

EFFECT: obtaining an infrared luminophor based on yttrium oxysulphide activated by erbium ions and co-activated by cerium ions, which has minimal visible anti-stokes luminescence when excited with laser radiation in the 0,90-0,98 mcm range and high intensity of stokes infrared luminescence in the 1,5-1,5 mcm range.

1 cl, 1 tbl, 12 ex

FIELD: printing industry.

SUBSTANCE: valuable document has marking, which contains luminescent compound that has both anti-stokes and Stocks law luminescence, with composition of Ln 1-X-Y-Z YbX ErY CeZ MeIC MeVID PI-D O4+D/2-C where: MeI - Li or Na, MeVI - W or Mo, Ln - Y, La, Gd, 0.1 ≤ x ≤ 0.9; 0.005 ≤ y ≤ 0.2; 0.0001 ≤ z ≤ 0.01; 0.001 ≤ c ≤ 0.1; 0.001 ≤ d ≤ 0.1; or compound of the following composition: Ln 2-X-Y-Z YbX ErY CeZ O2 S, where Ln - Y, La, Gd, 0 <x ≤ 0.2; 0.1 ≤ y ≤ 0.4; 0.0001 ≤ z ≤ 0.005; or compound of the following composition: Ln 2-X-Y-Z ErY CeZ O2 S; where Ln - Y, La, Gd, 0 < x ≤ 0.2; 0.1 ≤ y ≤ 0.4; 0.0001 ≤ z ≤ 0.005. Marking may be made by printing method, for instance offset method of printing. Method for identification of valuable document authenticity with all above mentioned criteria inherent in it includes detection of hidden protective marking on a valuable document by measurement and further analysis of dependency extent of stokes and anti-stokes luminescence strip intensity on density of excitation radiation capacity.

EFFECT: improved level of valuable document protection.

6 cl

FIELD: chemistry.

SUBSTANCE: invention relates to liquid crystal materials and can be used as flawless luminescent optical media in electro-optical and magneto-optical devices. A lyotropic liquid crystal composition is described, which contains oxyethylated surface active substance in form of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[29-hydroxy(3,6,9,12,15,18,21,24,27-oxanonacosaneoxy]-pentacyclo[19.3.-1.13,7.19,13.115,19]octacosa-1(25)3,5,7(28)9,11,13(27)15,17,19(26)21,13-dodecane, hexahydrate of europium nitrate and solvent in form of ethanol. Components of the composition are in the following ratio, wt %: said oxyethylated surface active substance - 55 to 79, hexahydrate of europium nitrate - 12 to 35, ethanol - 5 to 33.

EFFECT: production of lyotropic liquid crystal composition, with twelve times more luminescence efficiency and double the mean life of luminescent glow.

1 cl, 5 dwg, 1 tbl, 4 ex

FIELD: materials useful in agriculture, medicine, biotechnology, light industry.

SUBSTANCE: claimed material includes matrix and at least one light-converting compound, namely luminophor converting UV radiation into radiation of other colors and has particle size from 0.3 to 0.8 mum and general formula of MexaAybRzc, wherein Me is yttrium, lanthanum, cerium, praseodium, europium, gadolinium, dysprosium, erbium, ytterbium, aluminum, bismuth, manganese, calcium, strontium, barium, zinc, cesium; A is cerium, praseodium, europium, gadolinium, dysprosium, erbium, ytterbium, aluminum, indium and/or combination thereof; R is oxygen, sulfur, phosphorus, boron, vanadium, titanium, aluminum, indium and/or combination thereof; a, b and c represent charge of Me, A or R ions, respectively; x >=1; 1.0>=y>=0.0001; z corresponds ax+by=cz. Aldo disclosed is composition for material production containing abovementioned light-converting compound in amount of 0.001-10.0; and balance - matrix-forming component, e.g. polymer, fiber, varnish- or adhesive-forming agent.

EFFECT: conversion of UV irradiation of increased effectiveness; increased plant productivity.

16 cl, 21 ex

FIELD: chemistry.

SUBSTANCE: invention relates to liquid crystal materials and can be used as flawless luminescent optical media in electro-optical and magneto-optical devices. A lyotropic liquid crystal composition is described, which contains oxyethylated surface active substance in form of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[29-hydroxy(3,6,9,12,15,18,21,24,27-oxanonacosaneoxy]-pentacyclo[19.3.-1.13,7.19,13.115,19]octacosa-1(25)3,5,7(28)9,11,13(27)15,17,19(26)21,13-dodecane, hexahydrate of europium nitrate and solvent in form of ethanol. Components of the composition are in the following ratio, wt %: said oxyethylated surface active substance - 55 to 79, hexahydrate of europium nitrate - 12 to 35, ethanol - 5 to 33.

EFFECT: production of lyotropic liquid crystal composition, with twelve times more luminescence efficiency and double the mean life of luminescent glow.

1 cl, 5 dwg, 1 tbl, 4 ex

FIELD: printing industry.

SUBSTANCE: valuable document has marking, which contains luminescent compound that has both anti-stokes and Stocks law luminescence, with composition of Ln 1-X-Y-Z YbX ErY CeZ MeIC MeVID PI-D O4+D/2-C where: MeI - Li or Na, MeVI - W or Mo, Ln - Y, La, Gd, 0.1 ≤ x ≤ 0.9; 0.005 ≤ y ≤ 0.2; 0.0001 ≤ z ≤ 0.01; 0.001 ≤ c ≤ 0.1; 0.001 ≤ d ≤ 0.1; or compound of the following composition: Ln 2-X-Y-Z YbX ErY CeZ O2 S, where Ln - Y, La, Gd, 0 <x ≤ 0.2; 0.1 ≤ y ≤ 0.4; 0.0001 ≤ z ≤ 0.005; or compound of the following composition: Ln 2-X-Y-Z ErY CeZ O2 S; where Ln - Y, La, Gd, 0 < x ≤ 0.2; 0.1 ≤ y ≤ 0.4; 0.0001 ≤ z ≤ 0.005. Marking may be made by printing method, for instance offset method of printing. Method for identification of valuable document authenticity with all above mentioned criteria inherent in it includes detection of hidden protective marking on a valuable document by measurement and further analysis of dependency extent of stokes and anti-stokes luminescence strip intensity on density of excitation radiation capacity.

EFFECT: improved level of valuable document protection.

6 cl

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