Special optical glass with pure red luminous properties and its preparation method and application

Abstract

The invention discloses a special optical glass with pure red light emission characteristics, a preparation method and application thereof, and belongs to the technical field of special optical glass materials. The special optical glass of the present invention includes a glass matrix, and a reducing agent and a rare earth fluoride doped externally on the basis of the glass matrix; the chemical composition of the glass matrix is: a SiO 2 ‑bZnF 2 ‑cZnCl 2 ‑dLiF‑eMnF 2 ; In the formula, a, b, c, d, e are molar ratio numbers, and its values ​​are respectively: a is 40-50mol.%, b is 15-20mol.%, c is 10-15mol.%, d is 15mol.%, e is 0-15mol.%; the dosing amount of reducing agent is 0.05-3.0mol.%, and the dosing amount of rare earth fluoride is 0.1-2.0mol.%. The invention utilizes the characteristics of phase separation of fluorosilicate glass to regulate the performance of the glass from different dimensions, and finally obtains a special optical glass with good thermodynamic stability and high luminous efficiency. The special optical glass of the invention realizes the pure red light emission of rare earth ions, and can be applied to the fields of glass / optical fiber display, optical fiber temperature sensing, photodynamic therapy and the like.

Description

Technical field

[0001] The invention relates to the technical field of special optical glass materials, in particular to a special optical glass with pure red light emitting characteristics, a preparation method and application thereof. technical background

[0002] Rare earth ion up-conversion luminescence refers to the phenomenon that when rare earth ion doped luminescent materials are pumped by long wavelength excitation light, light with shorter wavelength than excitation light is emitted. However, the energy levels of rare earth ions are very rich. In the process of up-conversion luminescence pumped by excitation light source, light with multiple wavelength positions can usually be emitted at the same time. Therefore, it is of great significance to regulate the upconversion luminescence band of rare earth ion-doped luminescent materials for different application fields, especially in the red (600-700nm) and near-infrared (700-1100nm) spectral ranges, which are called "optica...

Examples

preparation example Construction

[0051] The preparation method of the special optical glass with pure red light emitting characteristics of the invention comprises the following steps:

[0052] (1) high purity (99.99%) silica (SiO 2 ), zinc fluoride (ZnF 2 ), zinc chloride (ZnCl 2 ), manganese fluoride (MnF 2 ), lithium fluoride (LiF), silicon nitride (Si 3 N 4 ) and high purity (99.99%) rare earth fluoride as raw materials to prepare glass mixture according to stoichiometric ratio;

[0053] (2) putting the raw materials weighed according to calculation in an agate jar, uniformly mixing them in a ball mill for 30-120min, and transferring the uniformly mixed raw materials into a Shi Ying crucible;

[0054] (3) Put the evenly mixed raw materials into a high-temperature furnace, melt them in the air atmosphere at 1200-1300℃ for 0.5-1.0h, and then pour the melt on the copper plate heated at 200℃ in advance for quenching, thus forming the substrate glass.

[0055] (4) Put the prepared glass in a precision annealing fu...

Embodiment 1

[0063] Example 1: 50 SiO 2 -15ZnF 2 -10ZnCl 2 -15LiF-xMnF 2 -1Si 3 N 4 -1YbF 3 -0.2ErF 3 Preparation of (x = 0-15, mol.%) fluorosilicate multicomponent glass

[0064] In the glass composition of this embodiment, SiO 2 、ZnF 2 、ZnCl 2 、LiF、MnF 2 As the glass matrix, the value before each compound represents the molar ratio (mol.%); Si 3 N 4 YbF, as an externally doped reducing agent, is 3 And ErF. 3 Is an externally doped rare earth ion, and the previous value represents the mole percentage of the doped rare earth ion relative to the whole glass matrix.

[0065] Specific preparation method: respectively weigh SiO according to the measured mass. 2 ，ZnF 2 ，ZnCl 2 ，LiF，MnF 2 ，Si3 N 4 And YbF 3 And ErF. 3 , put the above raw materials in agate jar and stir for 120min with ball mill to make them uniform. Transfer the evenly mixed raw materials to a Shi Ying crucible. Raise the temperature of the high-temperature furnace to 1300℃, and then put the Shi Ying crucible with cover containing r...

Embodiment 2

[0067] Example 2: 45 SiO 2 -15ZnF 2 -10ZnCl 2 -15LiF-xMnF 2 -1Si 3 N 4 -1YbF 3 -0.2HoF 3 Preparation of (x = 0,10,15, mol.%) fluorosilicate multicomponent glass

[0068] In the glass composition of this embodiment, SiO 2 、ZnF 2 、ZnCl 2 、LiF、MnF 2 As the glass matrix, the value before each compound represents the molar ratio (mol.%); Si 3 N 4 YbF, as an externally doped reducing agent, is 3 And HoF 3 Is an externally doped rare earth ion, and the previous value represents the mole percentage of the doped rare earth ion relative to the whole glass matrix.

[0069] Specific preparation method: respectively weigh SiO according to the measured mass. 2 ，ZnF 2 ，ZnCl 2 ，LiF，MnF 2 , Si3N4 and YbF 3 And HoF 3 , put the above raw materials in agate jar, and stir with ball mill for 60min to make them uniform. Transfer the evenly mixed raw materials to a Shi Ying crucible. Raise the temperature of the high-temperature furnace to 1250℃, then put the Shi Ying crucible with cover containing raw m...

Technical field

[0001] The invention relates to the technical field of special optical glass materials, in particular to a special optical glass with pure red light emitting characteristics, a preparation method and application thereof. technical background

[0002] Rare earth ion up-conversion luminescence refers to the phenomenon that when rare earth ion doped luminescent materials are pumped by long wavelength excitation light, light with shorter wavelength than excitation light is emitted. However, the energy levels of rare earth ions are very rich. In the process of up-conversion luminescence pumped by excitation light source, light with multiple wavelength positions can usually be emitted at the same time. Therefore, it is of great significance to regulate the upconversion luminescence band of rare earth ion-doped luminescent materials for different application fields, especially in the red (600-700nm) and near-infrared (700-1100nm) spectral ranges, which are called "optica...

Examples

preparation example Construction

[0051] The preparation method of the special optical glass with pure red light emitting characteristics of the invention comprises the following steps:

[0052] (1) high purity (99.99%) silica (SiO 2 ), zinc fluoride (ZnF 2 ), zinc chloride (ZnCl 2 ), manganese fluoride (MnF 2 ), lithium fluoride (LiF), silicon nitride (Si 3 N 4 ) and high purity (99.99%) rare earth fluoride as raw materials to prepare glass mixture according to stoichiometric ratio;

[0053] (2) putting the raw materials weighed according to calculation in an agate jar, uniformly mixing them in a ball mill for 30-120min, and transferring the uniformly mixed raw materials into a Shi Ying crucible;

[0054] (3) Put the evenly mixed raw materials into a high-temperature furnace, melt them in the air atmosphere at 1200-1300℃ for 0.5-1.0h, and then pour the melt on the copper plate heated at 200℃ in advance for quenching, thus forming the substrate glass.

[0055] (4) Put the prepared glass in a precision annealing fu...

Embodiment 1

[0063] Example 1: 50 SiO 2 -15ZnF 2 -10ZnCl 2 -15LiF-xMnF 2 -1Si 3 N 4 -1YbF 3 -0.2ErF 3 Preparation of (x = 0-15, mol.%) fluorosilicate multicomponent glass

[0064] In the glass composition of this embodiment, SiO 2 、ZnF 2 、ZnCl 2 、LiF、MnF 2 As the glass matrix, the value before each compound represents the molar ratio (mol.%); Si 3 N 4 YbF, as an externally doped reducing agent, is 3 And ErF. 3 Is an externally doped rare earth ion, and the previous value represents the mole percentage of the doped rare earth ion relative to the whole glass matrix.

[0065] Specific preparation method: respectively weigh SiO according to the measured mass. 2 ，ZnF 2 ，ZnCl 2 ，LiF，MnF 2 ，Si3 N 4 And YbF 3 And ErF. 3 , put the above raw materials in agate jar and stir for 120min with ball mill to make them uniform. Transfer the evenly mixed raw materials to a Shi Ying crucible. Raise the temperature of the high-temperature furnace to 1300℃, and then put the Shi Ying crucible with cover containing r...

Embodiment 2

[0067] Example 2: 45 SiO 2 -15ZnF 2 -10ZnCl 2 -15LiF-xMnF 2 -1Si 3 N 4 -1YbF 3 -0.2HoF 3 Preparation of (x = 0,10,15, mol.%) fluorosilicate multicomponent glass

[0068] In the glass composition of this embodiment, SiO 2 、ZnF 2 、ZnCl 2 、LiF、MnF 2 As the glass matrix, the value before each compound represents the molar ratio (mol.%); Si 3 N 4 YbF, as an externally doped reducing agent, is 3 And HoF 3 Is an externally doped rare earth ion, and the previous value represents the mole percentage of the doped rare earth ion relative to the whole glass matrix.

[0069] Specific preparation method: respectively weigh SiO according to the measured mass. 2 ，ZnF 2 ，ZnCl 2 ，LiF，MnF 2 , Si3N4 and YbF 3 And HoF 3 , put the above raw materials in agate jar, and stir with ball mill for 60min to make them uniform. Transfer the evenly mixed raw materials to a Shi Ying crucible. Raise the temperature of the high-temperature furnace to 1250℃, then put the Shi Ying crucible with cover containing raw m...

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