RU2610592C2 - LUMINOPHOR OF COMPLEX PRINCIPLE OF ACTION ON BASIS OF YTTRIUM, LANTHANUM AND GADOLINIUM OXYSULFIDES, ACTIVATED WITH IONS OF Yb3+ AND Tm3+ - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemical industry. Luminophor of complex action on based on oxysulfides of yttrium, lanthanum, gadolinium, activated with ions Tm³⁺ and sensitised ions Yb³⁺, has following chemical composition: (Ln_1-x-y-d-cYb_xTm_yMe¹ _dMe² _c)₂O₂S, where Ln is at least one of ions Y³⁺, La³⁺, Gd³⁺; Me¹ – of at least one ion of Group II elements of periodic table of elements – Ca²⁺, Sr²⁺, Ba²⁺; Me² – at least one of ions of elements IV (Ti⁴⁺, Zr⁴⁺, Si⁴⁺) or V (Nb⁵⁺, Ta⁵⁺) of groups of periodic table; 0.05≤x≤0.25; 0.0005≤y≤0.005; 0.01≤d≤0.1; 0.005≤c≤0.05. Invention provides increased photostimulated extinction of Stokes infrared luminescence of ions Yb³⁺ in region of 0.96–1.12 mcm, visible anti-Stokes and Stokes infrared luminescence of ions Tm³⁺ in region of 0.465–0.495 mcm, 0.79–0.84 mcm and 1.65–1.98 mcm without considerable change in spectral composition of initial radiation during combined effect of exciting infrared radiation in region of 0.94–0.98 mcm and stimulating radiation in region of 0.30–0.75 mcm.

EFFECT: invention can be used in making articles for detecting modulated radiation of multispectral composition.

1 cl, 4 dwg, 1 tbl, 19 ex

Description

The invention relates to the chemical industry and can be used to produce a new class of phosphors with a complex principle of operation, which, when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, are simultaneously effective photostimulated quenching Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without significant changes in spectral composition but the source radiation.

The phosphor of the complex principle of action based on yttrium, lanthanum, gadolinium oxysulfides has a chemical composition corresponding to the following empirical formula: (Ln _1-xydc Yb _x Tm _y Me ¹ _d Me ² _c ) ₂ O ₂ S, where Ln is at least one of ions Y ³⁺ , La ³⁺ , Gd ³⁺ ; Me ¹ - at least one of the ions of the elements of group II of the Periodic system D.I. Mendeleev - Ca ²⁺ , Sr ²⁺ , Ba ²⁺ ; Me ² - at least one of the ions of elements IV (Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ ) or V (Nb ⁵⁺ , Ta ⁵⁺ ) groups of the Periodic system D.I. Mendeleev; 0.05≤x≤0.25; 0,0005≤y≤0.005; 0.01 d d 0 0.1; 0.005≤c≤0.05.

Phosphor of the complex principle of action based on yttrium, lanthanum, gadolinium oxysulfides with simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm can be used in products designed to register modulated radiation of a multispectral composition, as well as to create new types of multispectral-sensitive products in which it is necessary to have a unique combination s multiple spectral-kinetic Parameter IR Stokes luminescence Yb ³⁺ ions in the 0.96-1.12 visible anti-Stokes and Stokes luminescence IR Tm ³⁺ ions in the areas of 0,465-0,495, and 0,79-0,84 1,65 -1.98 microns.

The purpose of the invention

The invention is aimed at creating a world-class new phosphor composition of a complex principle of action based on yttrium, lanthanum, gadolinium oxysulfides, which, when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0, 30-0.750 μm by simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1 , 65-1.98 μm without s nificant change in spectral composition of the radiation source. Under the phosphor of the complex principle of operation in this invention, it is customary to understand such a phosphor, during instrument control which is determined not one, but two or more spectrally kinetic parameters related to each other in a predetermined manner, for example, the intensity of several spectral bands of radiation in the visible and IR regions of the spectrum or the duration of the afterglow of these bands under the combined action of two or more exciting radiation, allowing for further machine processing of the obtained data s various hidden and hard-rasshifruemye codes or various combinations thereof.

The relevance and complexity of the task arises from the authors of this invention a generalized analysis of the currently known patent and journal data on phosphors based on yttrium oxysulfides and REE, which is given in chronological order below.

Current level

Luminophores based on yttrium, lanthanum and gadolinium oxysulfides are known, the chemical composition of which is described by the following generalized chemical formula:

Ln _(2-x) Ln ' _x O ₂ S,

where Ln - Y, La, Gd,

Ln 'is at least one of the elements of the group containing Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er,

0,0002≤x≤0,2.

(US Patent No. 4057507, CL C09K 11/46 of 11/08/1977; US Patent No. 4507560, CL H01J 1/62 of 03/26/1985; US Patent No. 4,510,414, CL C09K 11/08 of 04/09/1985; Patent US No. 5879587, CL C09K 11/84 dated 03/09/1999; US Patent No. 5958295, CL C09K 011/08 dated 09/28/1999; US Patent No. 6340436 B1, CL C09K 11/86 dated 01/22/2002; RU patent No. 2390535 C2, class C09K 11/77 dated 03/27/2010; Patent RU No. 2516129, class C09K 11/84 dated 04/20/2014).

The scope of their technical application is the production of color television picture tubes, various types of cathode ray tubes, X-ray screens, and securities protection.

The main disadvantage of the above phosphors is that they completely exclude the possibility of using them as a phosphor of the complex principle of operation with simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation, lies in the fact that the optically active rare-earth ions used in these phosphors (Ce ³⁺ , Pr ³⁺ , Nd ^{3 +} , Sm ³⁺ , Eu ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ ), which play the role of activating additives, when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm does not provide the required visible and IR luminescence in the areas of 0.465-0.495, 0.79-0.84, 0.96-1.12 and 1.65-1.98 microns. This drawback is of fundamental physical nature and is associated with the fundamental properties of the energy levels of the above rare-earth ions (GH Dicke. Spectra and energy levels of rare-earth ions in crystals. N.-Y. - London - Sydney - Toronto. 1968. 401 c.) .

Known phosphor based on lanthanum oxysulfide, activated by titanium ions, the chemical composition of which is described by the following chemical formula:

La _(2-x) Ti _x O ₂ S,

where 0.0001≤x≤0.05.

(US patent No. 3948798, CL C09K 11/46 from 04/06/1976).

The scope of its technical application is X-ray screens, fluorescent lamps.

The main disadvantage of the above phosphor, which completely excludes the possibility of using it as a phosphor of the complex principle of operation with simultaneous effective photostimulated quenching of visible and IR luminescence in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 and 1.65 -1.98 microns, lies in the fact that the optically active titanium ions used in this phosphor do not provide, when combined with exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns visible antisto x-ray and Stokes IR luminescence in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 and 1.65-1.98 μm. This drawback also has a fundamental physical character and is due to the fundamental properties of the energy levels of titanium ions (D.T. Sviridov, R.K. Sviridova, Yu.F. Smirnov. Optical spectra of transition metal ions in crystals. Science. 1976. 266 p. )

Known phosphor red glow with a long afterglow based on the oxysulfides Y, La, Gd, Lu, the chemical composition of which is described by the following chemical formula:

Ln ₂ O ₂ S: Eu _x , Me _y ,

where Ln - Y, La, Gd, Lu,

Me - Mg, Ti, Nb, Ta,

0.00001≤x≤0.5; 0.00001≤y≤0.3.

(US patent No. 6617781B2, CL H01J 1/62 of 09/09/2003).

The scope of its technical application is fluorescent lamps with a long afterglow.

The specified phosphor has the same drawback, namely, the lack of the required effective visible anti-Stokes and Stokes IR luminescence in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 and 1.65-1.98 μm at combined exposure to exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns. This disadvantage also has a fundamental physical character and is associated with the fundamental properties of activating additives.

Known infrared phosphors based on yttrium, lanthanum, gadolinium oxysulfides activated by Tm ³⁺ ions, the chemical composition of which is described by the following generalized chemical formula:

Ln _2-x Tm _x O ₂ S,

where Ln - Y, La, Gd, Lu,

0.002≤x≤0.2.

(French patent No. 2554122, class C09K 11/77 of 05/03/1985; Manashirov, O. Ya. Et al. Synthesis and study of solid solutions (Y _1-x Tm _x ) ₂ O ₂ S and their luminescence upon IR excitation // Inorganic materials. 2013.V. 49, No. 3. P. 281-286).

Their field of application is securities protection, production of multispectral-sensitive products of the latest generation, where a unique combination of several luminescent parameters is required.

The advantages of these infrared phosphors include:

- the ability to absorb stimulating radiation in the region of 0.30-0.750 μm due to the optical transition ³ H ₆ → ¹ D ₂ in the Tm ³⁺ ion;

- the ability to convert the absorbed radiation into the required Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.79-0.84, 1.65-1.98 μm due to optical transitions ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion.

The main disadvantages of the above infrared phosphors, which completely exclude the possibility of using it as an infrared phosphor of the complex principle of operation with simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 microns, visible anti-Stokes and Stokes IR luminescence of Tm ³ ions ⁺ in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, are as follows:

- the complete absence of Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 microns;

- the complete absence of visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm when exposed to exciting IR radiation in the region of 0.94-0.98 μm .

These shortcomings are also of a fundamental physical nature and are associated both with the absence of Yb ³⁺ ions in the phosphors and with the fundamental properties of Tm ³⁺ ions.

Known infrared phosphor based on yttrium oxysulfide, activated by Yb ³⁺ ions, the chemical composition of which is described by the following chemical formula:

(Y _1-x Yb ³⁺ _x ) ₂ O ₂ S,

0≤x≤1.

(O.Ya. Manashirov, E.M. Zvereva, V.A. Vorobyov. Comparative study of various classes of phosphors activated by Yb ³⁺ ions under IR excitation. Vestnik of the Southern Scientific Center of the Russian Academy of Sciences. 2012. V. 8, No. 4. C. . 38-49).

An analysis of the lighting parameters of the above-mentioned infrared phosphor has established that it is capable, thanks to Yb ³⁺ ions, of effectively converting the exciting IR radiation in the region of 0.94-0.98 μm due to the radiative transition ² F _5/2 → ² F _7/2 into the required Stokes IR radiation in the region of 0.96-1.12 microns. This unique feature of Yb ³⁺ ions has a fundamental physical character and consists in the fact that the energy of its only excited level ² F _5/2 approximately corresponds to the wavelength of the exciting radiation in the region of 0.94-0.98 μm, which provides the most favorable conditions for its absorption by a phosphor.

The main disadvantage of the known phosphor based on yttrium oxysulfide activated by Yb ³⁺ ions, completely excluding the possibility of its use as a phosphor of the complex principle of operation with simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 microns, visible Stokes and anti-Stokes luminescence IR Tm ³⁺ ions in areas of 0,465-0,495, 0,79-0,84 and 1,65-1,98 um without significantly changing the spectral composition of radiation source under the combined action of the exciting IR and radiation in the region of 0,94-0,98 mm and stimulating radiation in 0,30-0,750 mm, is apparent complete absence of anti-Stokes and Stokes luminescence IR Tm ³⁺ ions in areas of 0,465-0,495, and 0,79-0,84 1.65-1.98 microns. This drawback is also of fundamental physical nature and is associated with the fundamental properties of the energy levels of Yb ³⁺ ions in crystals (GH Dicke. Spectra and energy levels of rare-earth ions in crystals. N.-Y. - London - Sydney - Toronto. 1968. 401 c.).

Known phosphors based on yttrium, lanthanum, gadolinium oxysulfides activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions, the chemical composition of which is described by the following generalized chemical formula:

(Ln _1-xy Yb ³⁺ _x Tm _y ) ₂ O ₂ S,

where Ln - Y, La, Gd,

0.02≤x≤0.6, 0.0001≤y≤0.05.

(US Patent No. 6,686,074 B2, class B41M 3/12 dated 02/03/2004; Patent EP No. 1478715, class C09K 11/84 of 11/24/2004; Patent RU No. 2379192C1, class B42D 15/00 of 01/20/2010) .

Their area of application is securities protection.

An analysis of the lighting parameters of the above phosphors made it possible to establish that phosphors based on yttrium, lanthanum, and gadolinium oxysulfides activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions have the ability to absorb exciting IR radiation in the region of 0.94-0.98 μm due to optical transition ² F _7/2 → ² F _5/2 in the Yb ³⁺ ion and stimulating radiation in the region of 0.30-0.750 μm as a result of the optical transition ³ H ₆ → ¹ D ₂ in the Tm ³⁺ ion, and convert the absorbed radiation as a result of radiative transitions ² F _5/2 → ² F _7/2 in not Yb ³⁺ and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion into the desired visible anti-Stokes and Stokes IR luminescence of 0.465-0.495, 0.79-0.84, 0.96-1.12 and 1.65-1.98 μm when combined exposure to exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns.

The main disadvantage of the above phosphors based on yttrium, lanthanum, gadolinium oxysulfides activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions, completely excluding the possibility of their use as a phosphor of a complex principle of operation with simultaneous effective photostimulated quenching of Stokes IR luminescence of Yb ³⁺ ions in the region 0.96-1.12 microns, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 microns without a significant change in the spectral composition of the initial radiation, there is a complete absence of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1 , 65-1.98 μm when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm.

The magnitude (depth) of photostimulated quenching of IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, visible and IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1 , 98 microns for the above phosphors was determined by the formula:

where I _l is the intensity of the visible and IR luminescence bands in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 and 1.65-1.98 μm when exposed only to exciting IR radiation in region 0, 94-0.98 microns;

I _{l + s} is the intensity of visible and IR luminescence bands in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 and 1.65-1.98 μm when combined with exciting IR radiation in region 0 , 94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns.

The closest in technical essence and the achieved result to the claimed solution is the anti-Stokes phosphor based on yttrium, lanthanum, gadolinium oxysulfides activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions, the chemical composition of which is described by the following chemical formula:

(R _1-xy ) ₂ O ₂ S: Yb _x Tm _y ,

where R is Y, La, Gd,

0.2 х x 0 0.6; 0.0001≤y≤0.05.

(US patent No. 6841092 B2, CL C09K 11/08 from 09/19/2002).

The main area of its technical application is securities protection.

When combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the anti-Stokes phosphor proposed in the prototype provides the required anti-Stokes luminescence of Tm ³⁺ ions in the visible region at 0.435-0.495 μm and Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 microns and Tm ³⁺ ions in the regions of 0.79-0.84 and 1.65-1.98 microns due to radiative transitions ² F _{5 / 2} → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion (Fig. 1). Thus, the anti-Stokes phosphor proposed in the prototype fully complies with the technical requirements for the spectral composition of the radiation in the visible and IR spectral regions.

The main disadvantage of the prototype anti-Stokes phosphor based on yttrium, lanthanum, and gadolinium oxysulfides activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions, which completely excludes the possibility of its practical use as a phosphor with a complex principle of operation with simultaneous effective photo-stimulated quenching of Stokes IR luminescence ³⁺ in the region of 0.96-1.12 microns, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 microns without significant change the spectral composition of the initial radiation, there is a complete absence of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 microns, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0 , 84 and 1.65-1.98 μm when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm (Fig. 2).

Consider the main causes of the above disadvantages, the resulting problem points and new technical solutions aimed at eliminating them, which ultimately will distinguish the claimed invention from the prototype, as well as determine its novelty and inventive step.

Our theoretical analysis of the physical processes occurring in inorganic phosphors activated by rare-earth ions during single-photon excitation (IR radiation in the region of 0.94-0.98 μm) and two-photon excitation (combined exposure to exciting IR radiation in the region of 0.94-0, 98 microns and stimulating radiation in the region of 0.30-0.750 microns) allowed us to develop a unified conceptual approach to creating a new class of phosphors that provide effective photostimulated quenching of IR radiation generated by excitation 0,94-0,98 micrometers in the visible anti-Stokes and Stokes IR luminescence of rare earth ions by the action of the stimulating radiation in the UV 0,30-0,750 mm. According to this approach, to create a new phosphor of a complex principle of operation with simultaneous effective photostimulated quenching of the IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible and IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79 -0.84 and 1.65-1.98 μm based on yttrium, lanthanum, gadolinium oxysulfides, three conditions must be met.

The first condition provides for the presence in the phosphor as an activator and sensitizer of optically active ions, which, when excited by IR radiation in the region of 0.94-0.98 μm, provide the required Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm. To fulfill this condition, the phosphor of the complex principle of action must contain, as previously mentioned, simultaneously, as an activator and sensitizer, optically active ions Tm ³⁺ and Yb ^3+, respectively. In the phosphor proposed in the prototype, Tm ³⁺ and Yb ³⁺ ions are used as an activator and sensitizer, which fully corresponds to the first condition.

The second condition provides for the presence in the composition of the new phosphor of the complex principle of the action of ions forming donor levels in the band gap of the matrix of the IR phosphor (deep electron traps with a low probability of releasing electrons localized on them at room temperature). The formation of such traps can be achieved due to the partial heterovalent substitution of the cations of the matrix of the new IR phosphor with other ions having a large electron capture cross section. Analysis of thermal emission curves (TSL) of three-activator systems Ln ₂ O ₂ S: Yb ³⁺ , Tm, Me ^IV and Ln ₂ O ₂ S: Yb ³⁺ , Tm, Me ^V (where Me ^IV and Me ^V are elements of groups IV and V The periodic system of D.I. Mendeleev) shows that such ions can be Ti, Zr, Si, Nb, and Ta. In the phosphor proposed in the prototype, it was not proposed to use ions of the above elements, which essentially limits the functionality of the phosphor from a physical point of view.

The third condition provides for the presence in the composition of the proposed phosphor of the complex principle of the action of ions forming acceptor levels in the band gap of the IR phosphor matrix (deep hole traps with a low probability of releasing holes localized on them at room temperature). The formation of such traps can be achieved by heterovalently replacing the cations of the matrix of the new IR phosphor with other ions having a large hole capture cross section. Analysis of the TSL curves of three-activator systems Ln ₂ O ₂ S: Yb ³⁺ , Tm, Me ^II (where Me ^II is an element of group II of the Periodic Table of D.I. Mendeleev) made it possible to establish that such ions can be ions of Ca, Sr, and Wah. In the phosphor proposed in the prototype, it was not proposed to use ions of the above elements, which essentially limits the functionality of the phosphor from a physical point of view.

From the above data it follows that simultaneous effective photostimulated quenching of the IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible and IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1 , 65-1.98 μm without a significant change in the spectral composition of the initial radiation of a known phosphor based on Y, La, Gd oxysulfides activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions, when combined with exciting IR radiation in the range of 0.94-0 98 microns and stimulating radiation in the region of 0.30-0.750 microns can be achieved in Thu simultaneous presence in the phosphor, together with ions Tm ³⁺ and Yb ³⁺ one pair of said ions II and IV or II and V of the periodic system DI Mendeleev. In this case, the depth of photostimulated quenching and its kinetic parameters will be determined by the properties of the associated complex formed jointly by the ions Tm ³⁺ , Yb ³⁺ , Me ^II , Me ^IV or Me ^V , the probability of formation of which increases significantly with an increase in the concentration of ions of elements of groups II, IV or V Periodic system D.I. Mendeleev.

Summarizing the above, we can make a general conclusion that the anti-Stokes phosphor based on yttrium, lanthanum, and gadolinium oxysulfides proposed in the prototype does not meet the basic conditions for achieving the maximum photostimulated quenching depth of Stokes IR luminescence of Yb ³⁺ ions in terms of chemical composition, type of coactivating ions 0.96-1.12 micron region, visible anti-Stokes and Stokes luminescence IR Tm ³⁺ ions in areas of 0,465-0,495, 0,79-0,84 and 1,65-1,98 mm under the combined action of the exciting IR Light- Nia in 0,94-0,98 mm and stimulating radiation in 0,30-0,750 mm.

Thus, in the process of creating the invention claimed by the authors, well-known patents on phosphors based on yttrium and rare-earth oxysulfides activated by rare-earth ions were successively examined, their main disadvantages were identified, the main causes of their occurrence and the problem points arising from them were identified, new technical solutions were proposed and justified aimed at solving the problem points that distinguish the claimed invention from the prototype, i.e. are hallmarks.

The technical result that can be achieved using the present invention is reduced to a simultaneous substantial increase in the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 microns, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without significant changes in the spectral composition of the initial radiation when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0, 30-0.750 microns known anti Stokes phosphor based on yttrium, lanthanum, gadolinium oxysulfides activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions.

This technical result is achieved by the fact that it additionally contains in the cationic sublattice, as coactivating ions, a pair of ions of elements of the II and IV or II and V groups of the Periodic system D.I. Mendeleev and has a chemical composition corresponding to the following empirical formula:

(Ln _1-xydc Yb _x Tm _y Me ¹ _d Me ² _c ) ₂ O ₂ S,

where Ln is at least one of the ions Y ³⁺ , La ³⁺ , Gd ³⁺ ;

Me ¹ - at least one of the ions of the elements of group II of the Periodic system D.I. Mendeleev - Ca ²⁺ , Sr ²⁺ , Ba ²⁺ ;

Me ² - at least one of the ions of elements IV (Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ ) or V (Nb ⁵⁺ , Ta ⁵⁺ ) groups of the Periodic system D.I. Mendeleev;

0.05≤x≤0.25;

0,0005≤y≤0.005;

0.01 d d 0 0.1;

0.005≤c≤0.05.

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

1. The content of sensitizing ions of Yb ³⁺ in the inventive phosphor varies within 0.05≤x≤0.25;

2. The content of activating ions Tm ³⁺ in the inventive phosphor varies in the range of 0.0005≤y≤0.005;

3. As ions of elements of group II of the Periodic system D.I. Mendeleev in the inventive phosphor additionally used ions of Ca ²⁺ , Sr ²⁺ , Ba ²⁺ ;

4. The content of ions of elements of group II of the Periodic system D.I. Mendeleev Ca ²⁺ , Sr ²⁺ , Ba ²⁺ in the inventive phosphor varies in the range of 0.01 ≤ d 0 0.1;

5. As ions of the elements of group IV of the Periodic system D.I. Mendeleev in the inventive phosphor additionally used ions of Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ ;

6. The content of ions of the elements of group IV of the Periodic system D.I. Mendeleev's Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ in the inventive phosphor varies in the range of 0.005 с s 0 0.05;

7. As ions of elements of the V group of the Periodic system D.I. Mendeleev in the inventive phosphor additionally used ions Nb ⁵⁺ , Ta ⁵⁺ ;

8. The content of ions of the elements of group V of the Periodic system D.I. Mendeleev Nb ⁵⁺ , Ta ⁵⁺ in the inventive phosphor varies in the range of 0.005 ≤ s 0 0.05.

SUMMARY OF THE INVENTION

The essence of the claimed invention lies in the fact that the technical result is achieved provided that the entire combination of distinctive features is used:

1. The introduction into the cationic sublattice of the claimed phosphor of the complex principle of action of the above amounts of Tm ³⁺ ions optically active in the infrared region of the spectrum provides both maximum absorption of stimulating radiation in the region of 0.30-0.750 μm due to the optical transition ³ H ₆ → ¹ D ₂ in the ion Tm ³⁺ , as well as its effective conversion to the required visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.435-0.495, 0.79-0.84, 1.65-1.98 μm due to ³ G ₄ optical transitions → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ .

2. The introduction into the cationic sublattice of the claimed phosphor of the complex principle of action of the above amounts of optically active Yb ³⁺ ions provides both maximum absorption of IR radiation in the region of 0.94-0.98 μm, and its effective conversion due to the radiative transition ² F _5/2 → ² F _7/2 to the desired Stokes IR radiation in the region of 0.96-1.12 microns.

3. Introduction to the cationic sublattice of the claimed phosphor of the complex principle of the action of ions of elements of group II of the Periodic system Mendeleev’s Ca ²⁺ , Sr ²⁺ , and Ba ²⁺ ensures the formation in the band gap of the matrix of acceptor levels (deep hole traps with a low probability of releasing the holes localized on them at room temperature) with an optimal depth.

4. Introduction to the cationic sublattice of the claimed phosphor of the complex principle of action of the above amounts of ions of elements of group II of the Periodic system Mendeleev's Ca ²⁺ , Sr ²⁺ , and Ba ²⁺ provide the highest density of deep hole traps.

5. Introduction to the cationic sublattice of the claimed phosphor of the complex principle of the action of ions of elements of group IV of the Periodic system Mendeleev's Ti ⁴⁺ , Zr ⁴⁺ , and Si ⁴⁺ ensures the formation of donor levels in the band gap (deep electron traps with a low probability of release of electrons localized on them at room temperature) with an optimal depth.

6. Introduction to the cationic sublattice of the claimed phosphor of the complex principle of action of the above amounts of ions of elements of group IV of the Periodic system Mendeleev's Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ provides the highest density of deep electron traps.

7. Introduction to the cationic sublattice of the claimed phosphor of the complex principle of the action of ions of elements of group V of the Periodic system Mendeleev’s Nb ⁵⁺ , Ta ⁵⁺ ensures the formation in the band gap of the matrix of donor levels (deep electron traps with a low probability of releasing electrons localized on them at room temperature) with an optimal depth.

8. Introduction to the cationic sublattice of the claimed phosphor of the complex principle of action of the above amounts of ions of elements of group V of the Periodic system Mendeleev's Nb ⁵⁺ , Ta ⁵⁺ provides the highest density of deep electron traps.

9. Simultaneous introduction into the cationic sublattice of the claimed phosphor of the complex principle of action of Tm ³⁺ and Yb ³⁺ ions optically active in the infrared region and pairs of ions of elements II and IV (Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ ) or II and V (Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Nb ⁵⁺ , Ta ⁵⁺ ) groups of the Periodic system D.I. Mendeleev leads to the formation of an associative complex, which, when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, provides simultaneous and effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in region 0 , 96-1.12 microns, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 microns without significant changes in the spectral composition of the initial radiation.

10. Simultaneous introduction into the cationic sublattice of the claimed phosphor of the complex principle of the action of Tm ³⁺ and Yb ³⁺ ions and pairs of ions of elements II and IV (Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ti ^4+, optically active in the infrared region of the spectrum) , Zr ⁴⁺ , Si ⁴⁺ ) or II and V (Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Nb ⁵⁺ , Ta ⁵⁺ ) in the above amounts leads to the formation of associative complexes in optimal concentrations, providing when combined with exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm the greatest depth of the photostimulated carcass Nia IR Stokes luminescence Yb ³⁺ ions in the 0.96-1.12 micron, apparent anti-Stokes and Stokes luminescence IR Tm ³⁺ ions in areas 0,465-0,495, 0,79-0,84 and 1,65-1,98 μm without a significant change in the spectral composition of the initial radiation.

The quantitative limits indicated in the claims are for the ions Tm ³⁺ , Yb ³⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ , Nb ⁵⁺ , Ta ⁵⁺ included in the composition of the claimed IR phosphor, experimentally determined on the basis of the conditions for achieving as high intensity Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0, 79-0.84 and 1.65-1.98 microns with single-photon excitation by IR radiation in the region of 0.94-0.98 microns, and the maximum depth of photostimulated quenching of Stokes IR luminescence ion Yb ^{3+ s} in the region of 0.96-1.12 μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm when combined exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm (two-photon excitation).

Moreover, a decrease in the content of Tm ³⁺ and Yb ³⁺ ions to values lower than those indicated in the claims leads to a significant decrease in the intensity of Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 microns, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm with single-photon excitation by IR radiation in the region of 0.94-0.98 μm. An increase in the content of Tm ³⁺ and Yb ³⁺ ions to values greater than those indicated in the claims also leads to a significant decrease in the intensity of Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 microns, visible anti-Stokes and Stokes IR luminescence Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm with single-photon excitation by IR radiation in the region of 0.94-0.98 μm.

A decrease in the content of Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ , Nb ⁵⁺ , Ta ^{5+ ions} to values lower than those indicated in the claims leads to a significant decrease in the depth of the photostimulated quenching of Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm with the combined (two-photon) exposure to exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm.

Therefore, between the distinguishing features and the technical result of the claimed invention there is a causal relationship, because it is these signs that only in their totality ensure the achievement of the required technical result.

According to the information available to the authors, the set of essential features characterizing the essence of the claimed invention is not known from the achieved level of technology, which allows us to conclude that the invention meets the criterion of "novelty."

According to the authors, the essence of the claimed invention should not be explicitly for specialists from the achieved level of technology, because it does not reveal the above effect on the obtained technical result - a new property of the object - a set of features that distinguish the claimed invention from the prototype, which allows us to conclude that it meets the criterion of "inventive step".

The set of essential features characterizing the essence of the invention can be repeatedly used in the production of phosphors of a complex principle of action based on yttrium, lanthanum, gadolinium oxysulfides, which allows us to conclude that the invention meets the criterion of "industrial novelty".

The inventive phosphor of the complex principle of operation using the entire set of distinctive features is described by examples.

Example 1 (prototype)

The mixture for obtaining the phosphor of the prototype was prepared according to the following recipe:

Y ₂ O ₃ = 176.3 g

Yb ₂ O ₃ = 78.8 g

Tm ₂ O ₃ = 7.72 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

The indicated quantities of the charge components were loaded into a porcelain drum, porcelain balls with a diameter of 20 mm were added at the rate of 1 kg of balls per 1 kg of charge and mixed for 2 hours in a roller mill. The resulting mixture was loaded by slightly ramming into 0.8 L glass-carbon crucibles in a fume hood with ventilation. After the crucible was completely filled with a charge, it was closed with a glassy carbon lid and placed in a quartz bath with a capacity of 6 l from opaque quartz. The mixture was calcined in a KS-25 furnace at a temperature of 1150-1200 ° C for 2-3 hours in an atmosphere of nitrogen or inert gas. After the calcination time, the quartz baths with the charge were unloaded from the furnace and cooled in a metal fume hood. Glass-carbon crucibles were unloaded from quartz baths cooled to room temperature, a calcined phosphor was removed from them, which, under a fluorescent lamp (λ _max = 365 nm), was removed from the particles with a scalpel. Then the purified phosphor was placed in a container and washed with hot distilled water (60-70 ° C) by decantation until pH = 7-8 was reached. The phosphor washed with distilled water was loaded into a porcelain drum with balls and milled, depending on the size of the obtained product, in a roller mill for 10-15 minutes. The milled phosphor was transferred to a container, poured with a 5% aqueous solution of hydrochloric or nitric acid, and stirred for 10-15 minutes. After acid treatment, the phosphor was washed with distilled water to pH = 7, filtered and dried at a temperature of 110-120 ° C to a dusting state. After cooling to room temperature, the phosphor was sieved through a No. 76 sieve in a fume hood with ventilation. The chemical composition and depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns synthesized according to the prototype of the phosphor are given in table. one.

In the luminescence spectra of this phosphor (Fig. 2) in the visible and IR regions, both with single-photon excitation by 0.94 μm IR radiation and combined exposure to 0.94 μm exciting IR radiation and 0.365 μm stimulating radiation, the Stokes IR luminescence bands of Yb ions are observed ³⁺ in the region of 0.96-1.12 μm, visible anti-Stokes and Stokes IR luminescence bands of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm (radiative transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion). As can be clearly seen in FIG. 2, when switching from single-photon to two-photon excitation, the effect of photostimulated quenching of all the above visible and IR luminescence bands of Yb ³⁺ and Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns, and 1.65-1.98 μm for the known phosphor based on sodium oxysulfide activated with Tm ³⁺ ions and sensitized with Yb ³⁺ ions, composition (Y _0.78 ) ₂ O ₂ S: Yb _0.2 Tm _0.02 ( prototype) is not observed.

Example 2

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 193.0 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

TiO ₂ = 0.8 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of photostimulated quenching of the IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 microns, visible and IR luminescence of Tm ³⁺ ions in the regions of 0.465- 0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor (Fig. 3) in the visible and IR regions of the spectrum, both when single-photon excitation by IR radiation of 0.94 μm and when combined with exciting IR radiation of 0.94 μm and stimulating radiation of 0.365 μm, only characteristic Yb ions are observed ³⁺ and Tm ³⁺ visible anti-Stokes and Stokes IR luminescence bands in areas of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1.65-1.98 microns associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. As can be clearly seen in FIG. 3, with the combined action of exciting IR radiation of 0.94 μm and stimulating radiation of 0.365 μm for the resulting phosphor, the effect of photo-stimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, visible anti-Stokes and Stokes IR luminescence of Tm ions is observed ³⁺ in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle synthesized according to the claimed invention is 31, 43, 47 and 41%, respectively.

Example 3

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 188.5 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor (Fig. 4) in the visible and IR regions of the spectrum, both when single-photon excitation by 0.94 μm IR radiation and when combined with 0.94 μm exciting IR radiation and 0.365 μm stimulating radiation, only characteristic Yb ions are observed ³⁺ and Tm ³⁺ visible anti-Stokes and Stokes IR luminescence bands in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1.65-1.98 microns associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. As can be clearly seen in FIG. 4, under the combined effect of exciting IR radiation of 0.94 μm and stimulating radiation of 0.365 μm for the obtained phosphor, the effect of photo-stimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, visible anti-Stokes and Stokes IR luminescence of Tm ions is observed ³⁺ in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor synthesized according to the claimed invention of the complex principle of action is 40, 55, 58 and 53%, respectively.

Example 4

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 182.8 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

TiO ₂ = 8 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle synthesized according to the claimed invention is 33, 45, 49 and 42%, respectively.

Example 5

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 191.9 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 2 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle synthesized according to the claimed invention is 11, 21, 22 and 18%, respectively.

Example 6

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 182.8 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 10 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns synthesized according to the claimed invention, the phosphor of the complex principle of action is 25, 38, 39 and 31%, respectively.

Example 7

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 171.5 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 20 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 μm synthesized according to the claimed invention, the phosphor of the complex principle of action is respectively 35, 54, 57 and 46%.

Example 8

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 188.6 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.193 g

CaCO ₃ = 5 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle synthesized according to the claimed invention is 29, 42, 45 and 43%, respectively.

Example 9

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 187.6 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 1.93 g

CaCO ₃ = 5 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle synthesized according to the claimed invention is 50, 53, 54 and 59%, respectively.

Example 10

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 203.2 g

Yb ₂ O ₃ = 19.7 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 20 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle synthesized according to the claimed invention is 60, 73, 75 and 74%, respectively.

Example 11

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 158 g

Yb ₂ O ₃ = 98.5 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle of synthesis synthesized according to the claimed invention is 30, 20, 36, 35%, respectively.

Example 12

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

La ₂ O ₃ = 271.9 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns synthesized according to the claimed invention, the phosphor of the complex principle of action is respectively 50, 63, 65 and 65%.

Example 13

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Gd ₂ O ₃ = 301.9 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 μm synthesized according to the claimed invention, the phosphor of the complex principle of action is 44, 57, 59 and 49%, respectively.

Example 14

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 97.98 g

Gd ₂ O ₃ = 145 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

SrCO ₃ = 7.36 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle of action synthesized according to the claimed invention is 12, 12, 19 and 18%, respectively.

Example 15

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 90.32 g

La ₂ O ₃ = 141.4 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

BaCO ₃ = 9.85 g

TiO ₂ = 4 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 μm synthesized according to the claimed invention, the phosphor of the complex principle of action is 11, 10, 12 and 13%, respectively.

Example 16

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 22.58 g

Gd ₂ O ₃ = 253.75 g

La ₂ O ₃ = 11.078 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

ZrO ₂ = 6.15 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns synthesized according to the claimed invention, the phosphor of the complex principle of action is 15, 23, 20 and 27%, respectively.

Example 17

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 188.5 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

SiO ₂ = 3 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle of action synthesized according to the claimed invention is 12, 21, 18 and 17%, respectively.

Example 18

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 188.5 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

Nb ₂ O ₃ = 6.65 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns of the phosphor of the complex principle synthesized according to the claimed invention is 25, 45, 50 and 68%, respectively.

Example 19

The mixture to obtain the IR phosphor according to the claimed invention was prepared according to the following recipe:

Y ₂ O ₃ = 188.5 g

Yb ₂ O ₃ = 45.31 g

Tm ₂ O ₃ = 0.386 g

CaCO ₃ = 5 g

Ta ₂ O ₅ = 11.05 g

S = 130 g

Na ₂ CO ₃ = 70 g

LiF = 21 g

All other technological operations for the synthesis of this phosphor of the complex principle of operation were carried out according to example 1. The chemical composition and depth of the photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in areas of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm obtained according to the claimed invention IR phosphor are given in table. one.

In the luminescence spectra of this phosphor in the visible and IR spectral regions, both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in In the region of 0.30-0.750 μm, only the visible anti-Stokes and Stokes IR luminescence bands characteristic of Yb ³⁺ and Tm ³⁺ ions are observed in the regions of 0.465-0.495, 0.79-0.84, 0.96-1.12 microns and 1 , 65-1.98 μm, associated with optical transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the Tm ³⁺ ion. Under the combined effect of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm, the effect of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the range of 0.96-1.12 is observed for the obtained phosphor μm, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 μm without a significant change in the spectral composition of the initial radiation. According to the table. 1, the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1, 65-1.98 microns synthesized according to the claimed invention, the phosphor of the complex principle of action is 10, 13, 12 and 13%, respectively.

Thus, the above examples indicate that the joint introduction into the composition of phosphors based on yttrium, lanthanum, gadolinium oxysulfides in the amounts of Yb ³⁺ and Tm ³⁺ ions optically active in the visible and IR regions and pairs from ions of elements II and IV (Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ ) or II and V (Ca ²⁺ , Sr ²⁺ , Ba, Nb, Ta ^{e +} ) groups of the Periodic system D .AND. Mendeleev makes it possible to significantly increase the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 microns, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1 , 65-1.98 microns without a significant change in the spectral composition of the initial radiation when combined with exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns and create a new one that has no analogues in world practice class of phosphors of the complex principle of action with a single mennym effective photostimulated luminescence quenching Stokes IR Yb ³⁺ ions in the 0.96-1.12 micron, apparent anti-Stokes and Stokes luminescence IR Tm ³⁺ ions in areas 0,465-0,495, and 0,79-0,84 1,65- 1.98 μm, which is characterized by the following unique combination of spectral-kinetic properties, namely:

- a predetermined and reproducible position in the stationary luminescence spectrum of the new phosphor of the complex principle of operation both with single-photon excitation by IR radiation in the region of 0.94-0.98 μm, and with the combined action of exciting IR radiation in the region of 0.94-0.98 μm and stimulating radiation in the region of 0.30-0.750 μm of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 microns, visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0, 84 and 1.65-1.98 μm (radiative transitions ² F _5/2 → ² F _7/2 in the Yb ³⁺ ion and ³ G ₄ → ³ H ₆ ; ³ H ₄ → ³ H ₆ ; ³ F ₄ → ³ H ₆ in the ion Tm ³⁺ );

- the depth of photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79- significantly increased compared with the known infrared phosphors 0.84 and 1.65-1.98 microns when combined with exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns;

- the predetermined and reproducible nature of the change in the intensity of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1 , 65-1.98 microns from the power density of the exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns;

- the predetermined and reproducible nature of the change in the duration of the acceleration and decay of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0, 84 and 1.65-1.98 microns after applying and removing exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns;

- the predetermined and reproducible nature of the change in the duration of the acceleration and decay of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0, 84 and 1.65-1.98 microns from the power density of the exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns;

- the predetermined and reproducible nature of the change in the response time of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12 μm, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 microns from the power density of the exciting IR radiation in the region of 0.94-0.98 microns and stimulating radiation in the region of 0.30-0.750 microns.

All of the listed properties of the new phosphor of the complex principle of action are determined by the fundamental physical properties of the phosphor matrix (Ln ₂ O ₂ S) (band gap, space group, local symmetry of the cation, etc.), the energy structure of Yb ³⁺ and Tm ³⁺ ions and element ions II, IV and V groups of the Periodic system D.I. Mendeleev and therefore have a given and reproducible character. All the proposed properties of the new IR phosphor can be used to register modulated emission of a multispectral composition, as well as to create new types of multispectral-sensitive products both individually and in various combinations. The use of the new phosphor of the complex principle of operation with such a unique set of properties will allow for the first time in world practice to use their combination as an original set of features to qualitatively increase the degree of protection of multispectrally sensitive products.

The above set of spectral and kinetic properties of the new phosphor of the complex principle of operation with simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0 , 79-0.84 and 1.65-1.98 microns are not found in the known technical solutions and for this reason cannot be imitated by the technical solutions known from the prior art either individually or in any combination.

The developed new phosphor of the complex principle of operation with simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0, 84 and 1.65-1.98 microns are also characterized by the following set of physico-chemical and technological parameters:

- high hydrolytic resistance;

- high thermal stability;

- high chemical resistance;

- hardness not higher than 7 points on the Mohs scale;

- average particle size of 5-15 microns.

A new phosphor of the complex principle of operation with simultaneous effective photostimulated quenching of the Stokes IR luminescence of Yb ³⁺ ions in the region of 0.96-1.12, the visible anti-Stokes and Stokes IR luminescence of Tm ³⁺ ions in the regions of 0.465-0.495, 0.79-0.84 and 1.65-1.98 microns and the technology of its manufacture during 2013-2014. passed several cycles of experimental and pilot industrial tests at enterprises producing multispectral-sensitive products. According to the test results, the developed phosphor of the complex principle of action meets all the requirements and is recommended for industrial production.

Claims (9)

The phosphor of the complex principle of action based on yttrium, lanthanum, gadolinium oxysulfides, activated by Tm ³⁺ ions and sensitized by Yb ³⁺ ions, characterized in that it additionally contains a pair of ions of elements II and IV or II and, in the cationic sublattice, as coactivating ions V groups of the Periodic system D.I. Mendeleev and has a chemical composition corresponding to the following empirical formula: (Ln _1-xydc Yb _x Tm _y Me ¹ _d Me ² _c ) ₂ O ₂ S, where Ln is at least one of the ions Y ³⁺ , La ³⁺ , Gd ³⁺ ; Me ¹ - at least one of the ions of the elements of group II of the Periodic system D.I. Mendeleev - Ca ²⁺ , Sr ²⁺ , Ba ²⁺ ; Me ² - at least one of the ions of elements IV (Ti ⁴⁺ , Zr ⁴⁺ , Si ⁴⁺ ) or V (Nb ⁵⁺ , Ta ⁵⁺ ) groups of the Periodic system D.I. Mendeleev; 0.05≤x≤0.25; 0,0005≤y≤0.005; 0.01 d d 0 0.1; 0.005≤c≤0.05.

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