1. The erbium-doped phosphate laser glass is characterized by comprising the following raw material components in percentage by mole:

r is Mg, Ca and Ba; ra is Na and K; (RO + Ra)₂O)/P₂O₅Greater than or equal to 0.8, RO by RCO₃And R (H)₂PO₄)₂Introduction of Ra₂O through RaPO₃Introduction of Al₂O₃By Al₂O₃Or Al (H)₂PO₄)₃And (4) introducing.

2. A preparation method of erbium-doped phosphate laser glass is characterized by comprising the following steps:

weighing, grinding and melting the raw material components and the mol percentage of the erbium-doped phosphate laser glass in claim 1 to obtain glass liquid;

secondly, pouring the molten glass on a preheated iron mold to obtain a transparent and uniform glass precursor;

thirdly, transferring the glass precursor into a muffle furnace for annealing treatment, wherein the annealing temperature is the glass transition temperature T_gAfter preserving heat for 3-24 hours, cooling to room temperature at a cooling rate of 0.1-10 ℃/h, and taking out a glass precursor;

and fourthly, processing the glass precursor obtained in the third step into a glass sheet with the thickness of 1-2 mm.

3. The method for preparing erbium-doped phosphate laser glass according to claim 2, wherein the grinding and melting in the step (r) are carried out by putting raw materials into an agate mortar for fully grinding to form mixed powder; and then placing the mixed powder into a crucible, putting the crucible into a melting furnace at 1100-1200 ℃ for melting for 60-70 min, and melting to obtain glass liquid.

4. A method for preparing erbium-doped phosphate laser glass according to claim 3, wherein the crucible is a corundum or platinum crucible.

5. An optical element comprising the erbium-doped phosphate laser glass according to any one of claims 1 to 4.

Technical Field

Ultra-wideband fiber amplifiers have a greater number of channels and a greater bandwidth, and are therefore of great interest in the field of optical communications. Er³⁺Ions are widely used as optical amplification media because they are in the lowest loss window of single-mode optical fibers. But commonly used L-band Er-doped³⁺The working wavelength of the optical fiber amplifier is 1570-1603 nm, and the optical fiber amplifier is not expanded to an L + wave band (1603 nm-1627 nm).

The current novel host material optical fiber amplifier comprises Er-doped³⁺The tellurium-based fiber amplifier (EDTFA) can work in a C + L wave band or an L wave band (1581-1616 nm). The gain bandwidth of EDTFA in the L band is large, but the high refractive index of EDTFA causes high nonlinear effect, and the raw material cost is high. The phosphate glass has high solubility to rare earth ions, large gain per unit length, low cost of raw materials, good fiber forming performance and suitability for civil communication, and is used for small optical fiber amplifiers. The invention proposes a method for modifying (RO + R) in phosphate glasses₂O)/P₂O₅To expand Er³⁺To 1627nm and provides a preparation flow.

Disclosure of Invention

The invention aims to provide erbium-doped phosphate laser glass which has the advantages of low cost, easiness in preparation, high doping concentration and the like, and a corresponding preparation method.

The technical solution of the invention is as follows:

the composition of an erbium-doped phosphate laser glass is described as follows:

r ═ Mg, Ca, Ba, Ra ═ Na, K, where (RO + Ra)₂O)/P₂O₅Greater than or equal to 0.8. The luminous intensity at 1627nm is greater than 1/2 which is the magnitude of luminous intensity at 1603 nm.

The invention also provides a preparation method of the erbium-doped phosphate laser glass, which comprises the following steps:

calculating and weighing raw materials according to the composition and the mole percentage of the erbium phosphate laser glass in claim 1, and putting the raw materials into an agate mortar for fully grinding to form mixed powder;

placing the mixed powder obtained by grinding in the step I into a corundum crucible, putting the corundum crucible into a 1100-1200 ℃ smelting furnace, and smelting for 60-70 min to obtain glass liquid;

thirdly, pouring the glass liquid on a preheated iron mold to obtain a transparent and uniform glass precursor;

fourthly, transferring the glass precursor into a muffle furnace for annealing treatment, wherein the annealing temperature is the glass transition temperature (T)_g) After preserving heat for 3-24 hours, cooling to room temperature at a cooling rate of 0.1-10 ℃/h, and taking out a glass precursor;

and fifthly, processing the glass precursor obtained in the step IV into a glass sheet with the thickness of 1-2 mm.

The glass sheet may be ground or polished to obtain optical elements such as lenses and prisms.

The invention has the technical effects that:

the invention controls Er³⁺(RO + R) in phosphate-doped glass₂O)/P₂O₅To increase Er³⁺Local field strength of the ion, thereby increasing Er³⁺Stark splitting and asymmetry of (1), and ultimately Er³⁺The fluorescence bandwidth of the ions is extended. RO and R₂O as a component of the glass network modifier acts to break or accumulate the glass network, and the glass network modifier P is modified by the change of the O and the network modifier₂O₅The proportion of Er can be easily changed³⁺The degree of order of the lattice sites. Er³⁺The lower the degree of order of the local environment, the larger the difference of the stark energy levelsThe wider the fluorescence line. In addition, the glass has the advantages of low cost, easy preparation, high doping concentration and the like, and can be used in high-power high-energy pulse laser media.

Drawings

FIG. 1 shows Er at room temperature in example 1#, example 2#, example 3#, and example 4# of the present invention³⁺The fluorescence spectrum of (1) is illustrated by Er in each example³⁺Change in the ratio of fluorescence intensity at 1627nm and 1603 nm.

FIG. 2 shows example 3 of the present invention, Er of another erbium-doped phosphate glass and erbium-doped quartz glass at room temperature³⁺The emission spectrum of (a).

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.

The components of the examples of erbium-doped phosphate laser glass of the present invention are as follows:

table 1: formulation of the example Components

Example 1 #:

the raw materials are shown in table 1, and the specific preparation process is as follows:

weighing raw materials (70 g in total):

placing the weighed raw materials in an agate mortar for fully grinding to form mixed powder, placing the ground mixed powder in a corundum crucible, placing the corundum crucible in a high-temperature furnace at 1150 ℃ for melting for 55min, and raising the temperature to 1200 DEG CAnd keeping the temperature for about 10 min. Thereafter, the homogeneous molten glass is cast on a preheated cast iron mould, which is transferred rapidly to an annealing furnace after its shaping, at about T_gAnnealing at temperature for 180min followed by cooling to room temperature at a rate of about 1 deg.C/min. In the melting process, a corundum crucible is required to be covered, so that the volatilization of raw materials is reduced. The prepared glass precursor is processed into a glass sheet with the thickness of 1 mm.

Example 2 #:

the raw materials are shown in table 1, and the specific preparation process is as follows:

weighing raw materials (70 g in total):

the weighed raw materials are placed in an agate mortar to be fully ground to form mixed powder, the mixed powder obtained by grinding is placed in a corundum crucible, and is placed in a high-temperature furnace at 1150 ℃ to be melted for 55min, and then the temperature is raised to 1200 ℃ and is kept for 10 min. Thereafter, the homogeneous molten glass is cast on a preheated cast iron mould, which is transferred rapidly to an annealing furnace after its shaping, at about T_gAnnealing at temperature for 180min followed by cooling to room temperature at a rate of about 1 deg.C/min. In the melting process, a corundum crucible is required to be covered, so that the volatilization of raw materials is reduced. The prepared glass precursor is processed into a glass sheet with the thickness of 1 mm.

Example 3 #:

the raw materials are shown in table 1, and the specific preparation process is as follows:

weighing raw materials (70 g in total):

the weighed raw materials are placed in an agate mortar to be fully ground to form mixed powder, the mixed powder obtained by grinding is placed in a corundum crucible, and is placed in a high-temperature furnace at 1150 ℃ to be melted for 55min, and then the temperature is raised to 1200 ℃ and is kept for 10 min. Thereafter, the homogeneous molten glass is cast in a preheated stateOn cast iron moulds, and after shaping, rapidly transferring to an annealing furnace at about T_gAnnealing at temperature for 180min followed by cooling to room temperature at a rate of about 1 deg.C/min. In the melting process, a corundum crucible is required to be covered, so that the volatilization of raw materials is reduced. The prepared glass precursor is processed into a glass sheet with the thickness of 1 mm.

Example 4 #:

the raw materials are shown in table 1, and the specific preparation process is as follows:

weighing raw materials (70 g in total):

the weighed raw materials are placed in an agate mortar to be fully ground to form mixed powder, the mixed powder obtained by grinding is placed in a corundum crucible, and is placed in a high-temperature furnace at 1150 ℃ to be melted for 55min, and then the temperature is raised to 1200 ℃ and is kept for 10 min. Thereafter, the homogeneous molten glass is cast on a preheated cast iron mould, which is transferred rapidly to an annealing furnace after its shaping, at about T_gAnnealing at temperature for 180min followed by cooling to room temperature at a rate of about 1 deg.C/min. In the melting process, a corundum crucible is required to be covered, so that the volatilization of raw materials is reduced. The prepared glass precursor is processed into a glass sheet with the thickness of 1 mm. The glass sheet may be ground or polished to obtain optical elements such as lenses and prisms.

Effect embodiment:

FIG. 1 shows Er in the example³⁺Fluorescence spectrum in the wavelength band of 1600 to 1635 nm. As can be seen from the inset, Er at room temperature is observed in example 1#, example 2#, example 3#, and example 4#³⁺The fluorescence intensity ratios at 1627nm and 1603nm are 0.5402, 0.5640, 0.5862 and 0.6038 respectively, which are all higher than 0.5. As can be seen, the fluorescence bandwidth of the invention in the L + band is flatter.

Formulation of other matrix components and Er at room temperature³⁺The ratio of fluorescence intensity at 1627nm and 1603nm is as follows:

comparative example 1:

phosphate saltsGlass: 72P₂O₅-8Al₂O₃-20BaO-0.5Er₂O₃，I₁₆₂₇/I₁₆₀₃＝0.3538

Comparative example 2:

quartz: 0.05Er₂O₃-0.5Al₂O₃-99.45SiO₂，I₁₆₂₇/I₁₆₀₃＝0.5283

As shown in FIG. 2, Er of example 3#³⁺The normalized fluorescence intensity ratio at 1627nm and 1603nm was 0.5862, Er of the erbium-doped quartz glass of comparative example 1³⁺The normalized fluorescence intensity ratio at 1627nm and 1603nm was 0.5283, Er for the erbium-doped phosphate glass of comparative example 2³⁺The normalized fluorescence intensity ratio at 1627nm and 1603nm was 0.3538. In contrast, example 3# has a much flatter spectrum in the L + band.