L-band luminescence-enhanced erbium-doped silicate glass and application thereof

Abstract

The invention discloses L-band luminescence enhanced erbium-doped silicate glass and a preparation method thereof, provides a method for calculating an emission cross section sigma e1600 through the effective field intensity E of the glass, and aims to solve the problems of low Er < 3 + > ion emission cross section and small gain coefficient in an erbium-doped optical fiber. The silicate glass is prepared from the following molar components: 44 to 79.2 mol percent of SiO2, 0 to 12.5 mol percent of Al2O3, 0 to 13 mol percent of Y2O3, 0 to 11.8 mol percent of La2O3, 0 to 25 mol percent of MgO, 0 to 8 mol percent of CaO, 0 to 9.8 mol percent of SrO, 0 to 9 mol percent of BaO, 0 to 60 mol percent of Li2O, 0 to 60 mol percent of Na2O, 0 to 10 mol percent of K2O and 0.1 to 3 mol percent of Er2O3. Experiments show that the emission cross section of the erbium-doped silicate glass in the L wave band is improved by means of improving the field intensity of the glass, optimizing the local structure and the like, and meanwhile, the gain of the erbium-doped optical fiber in the L wave band is improved. The method can be used for expanding the communication bandwidth, and has important application value for development of the fields of next generation telecommunication systems, wind power laser radars, quantum internet and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of optical fibers and relates to an erbium-doped silicate glass with enhanced L-band luminescence. Technical Background

[0002] The L-band erbium-doped laser operates at a wavelength of 1565-1625nm and has important applications in the next generation of telecommunication systems, wind power lidar, quantum Internet, etc. With the development of communication technology, the demand for the expansion of data transmission capacity is growing. Currently, most commercial erbium-doped fiber amplifiers are made of quartz. However, this quartz-based erbium-doped fiber amplifier is affected by the Er in the fiber in the L-band. 3+ The limitation of low emission cross section leads to low gain coefficient, and the gain bandwidth must be expanded in order to increase transmission capacity.

[0003] Multi-component glass fiber has become an attractive fiber matrix for L-band erbium-doped fiber due to its wide spectral tuning range. Tellurite fiber has disadvantages such as easy crystallization during the preparation process and expensive raw materials. Phosphate fiber is limited by poor chemical stability, resulting in poor fiber uniformity. In contrast, silicate glass has obvious advantages in physical and chemical stability, preparation process and cost. Chinese patent CN117466539A discloses a technical solution using silicate glass as a fiber gain medium, by introducing alkali metals and alkaline earth metals to increase Er 3+ ions in the extended L-band. However, this technique does not specifically reveal the effect of glass composition on Er 3+ Therefore, the effect of glass components on Er 3+ The method of regulating the local structure of ions is useful for further improving Er 3+ The emission performance of ions in the L-band has important technical significance and application value. Summary of the invention

[0004] In order to overcome the shortcomings and difficulties of the prior art as much as possible, the present invention aims to provide an Er-doped silicate glass with enhanced L-band luminescence, and to study the effect of network exosome cations in the glass on Er 3+ The mechanism of the influence of the local structure of ions is proposed, and a method for calculating the emission cross section σ through the effective field strength E of the glass is proposed. e1600 method.

[0005] The invention provides an L-band luminescence-enhanced erbium-doped silicate glass, wherein the molar composition range of the silicate glass is: SiO2: 44-79.2mol%, Al2O3: 0-12.5mol%, Y2O3: 0-13mol%, La2O3: 0-11.8mol%, MgO: 0-25mol%, CaO: 0-8mol%, SrO: 0-9.8mol%, BaO: 0-9mol%, Li2O: 0-60mol%, Na2O: 0-60mol%, K2O: 0-10mol%, and Er2O3: 0.1-3mol%.

[0006] In a further optimized scheme, the composition and molar content of the silicate glass are: SiO2: 44mol%, Al2O3: 12.5mol%, Y2O3: 2.5mol%, La2O3: 11.8mol%, MgO: 13.2mol%, CaO: 0mol%, SrO: 0mol%, BaO: 0mol%, Li2O: 9.6mol%, Na2O: 0mol%, K2O: 5.4mol%, Er2O3: 1.0mol%. The effective field strength is 0.35×10 -16 cm -2 The emission cross section at 1600nm wavelength reaches 23.5×10 -22 cm 2 .

[0007] In a further optimized scheme, the composition and molar content of the silicate glass are: SiO2: 44mol%, Al2O3: 10.5mol%, Y2O3: 4.5mol%, La2O3: 7.2mol%, MgO: 8mol%, CaO: 0mol%, SrO: 9.8mol%, BaO: 0mol%, Li2O: 8.2mol%, Na2O: 6.8mol%, K2O: 0mol%, Er2O3: 1.0mol%. The effective field strength is 0.31×10 -16 cm -2 The emission cross section at 1600nm wavelength reaches 19.1×10 -22 cm 2 .

[0008] In a further optimized scheme, the composition and molar content of the silicate glass are: SiO2: 59mol%, Al2O3: 0mol%, Y2O3: 0mol%, La2O3: 0mol%, MgO: 25mol%, CaO: 0mol%, SrO: 0mol%, BaO: 0mol%, Li2O: 0mol%, Na2O: 15mol%, K2O: 0mol%, Er2O3: 1.0mol%. The effective field strength is 0.29×10 - 16 cm -2 , the emission cross section at 1600nm wavelength reaches 14.3×10 -22 cm 2 .

[0009] The present invention studies the effect of the network external cation field strength on Er in silicate glass. 3+ Regulation mechanism of ion local structure and spectral properties, Er in silicate glass 3+ The second coordination ion of the ion is the network extracellular cation, and the field strength of the network extracellular cation affects Er 3+ The local environment of ions, high field strength network external cations and Er 3+ The ions have fewer coordination numbers. The higher the effective field strength E in the glass, the larger the emission cross section, and there is a linear relationship between the two. Therefore, a method is proposed to calculate the emission cross section σe by the effective field strength E of the glass. 1600 The calculation formula of the effective field strength E of glass proposed in this paper is as follows:

[0010]

[0011] Where i is the type of network extracellular cations in the glass, and B represents the Er in the glass calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordination ion, A is the field strength of the network cation in the glass, which is obtained by dividing the cation valence by the square of the distance between the cation and oxygen. The effective field strength E of all glasses is used as the horizontal coordinate and the emission cross section σe at a wavelength of 1600nm 1600 Draw a scatter plot as the ordinate, and do a linear fit to get the effective field strength through the glass to calculate the glass emission cross section:

[0012] σ e1600 =-19.6+120E, where the coefficient of determination R 2 =92.6%

[0013] The present invention also provides a direct sintering preparation method of the silicate glass, which is characterized by comprising the following steps:

[0014] (1) Ingredients: wherein SiO2: 44-79.2 mol%, Al2O3: 0-12.5 mol%, Y2O3: 0-13 mol%, La2O3: 0-11.8 mol%, MgO: 0-25 mol%, CaO: 0-8 mol%, SrO: 0-9.8 mol%, BaO: 0-9 mol%, Li2O: 0-60 mol%, Na2O: 0-60 mol%, K2O: 0-10 mol%, Er2O3: 0.1-3 mol%, convert the molar ratio of each oxide into mass fraction, weigh the mass fraction of the corresponding oxide raw materials, and fully mix them to form a glass batch;

[0015] (2) Melting: The mixed glass batch is placed in a crucible and melted at 1300°C to 1450°C; during the glass melting process, water is removed by ventilation and oxygen is continuously introduced for 1 to 3 hours; the glass melt is poured into a preheated iron mold for molding;

[0016] (3) Annealing: The glass is placed in an annealing furnace for annealing at a temperature of 450 to 580° C. for 3 to 5 hours, and then cooled to room temperature to obtain the silicate glass.

[0017] The L-band luminescence-enhanced erbium-doped silicate glass of the present invention can be used as a glass material for preparing Er-doped silicate optical fiber, and is used to improve the gain bandwidth of erbium-doped silicate optical fiber in the L-band and expand the communication bandwidth. It has important application value for the development of next-generation telecommunication systems, wind laser radar, quantum Internet and other fields.

[0018] Technical effects of the present invention:

[0019] 1. The present invention enhances the Er 3+ Using network modifier cations to change the luminescence properties of Er 3+ The local structure and coordination mode in silicate glass change its spectral properties and obtain a wavelength greater than 20×10 -22 cm 2 The emission cross section solves the problem of Er 3+ The problem of low emission cross section of ions in the L-band is solved, thereby achieving the beneficial effect of significantly improving the gain bandwidth of erbium-doped silicate glass.

[0020] 2. The present invention proposes a method for calculating the emission cross section σ through the effective field strength E of glass e1600 The method satisfies the formula: σ e1600 =-19.6+120E, where the coefficient of determination R 2 =92.6%.

[0021] 3. The optical fiber made of erbium-doped silicate glass with enhanced L-band luminescence of the present invention obtains a gain of more than 20 dB in the L-band, improves the L-band gain bandwidth, can be used to expand the communication bandwidth, and has important application value for the development of next-generation telecommunication systems, wind laser radar, quantum Internet and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the normalized fluorescence spectra of Examples 1#-3# of the present invention;

[0023] Figure 2 The emission spectra of Examples 1#-3# of the present invention at 1600nm;

[0024] Figure 3 is the normalized fluorescence spectra of Examples 4#-6# of the present invention;

[0025] Figure 4 The emission spectra of Examples 4#-6# of the present invention at 1600nm;

[0026] Figure 5 The normalized fluorescence spectra of Example 2 and Examples 7#-11# of the present invention;

[0027] Figure 6 The emission spectra of Example 2 and Examples 7#-11# of the present invention at 1600nm;

[0028] Figure 7 is the normalized fluorescence spectra of Examples 11#-15# of the present invention;

[0029] Figure 8 The emission spectra of Examples 11#-15# of the present invention at 1600nm;

[0030] Fig. 9 This is a graph showing the relationship between the effective field strength and the emission cross section of embodiments 1#-15# of the present invention;

[0031] Fig.10 ASE diagrams of optical fibers prepared in Example 7# and Example 10# of the present invention;

[0032] Fig.11 This is the gain diagram of the optical fiber prepared in Example 7# and Example 10# of the present invention. DETAILED DESCRIPTION

[0033] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, without departing from the present invention, some modifications and improvements can be made. These all belong to the protection scope of the present invention.

[0034] The doping components, effective field intensity and emission cross section of 15 embodiments of an L-band luminescence enhanced erbium-doped quartz glass are shown in Table 1. 3+ The coordination numbers of ions and secondary coordinated ions are shown in Table 2.

[0035]

[0036]

[0037] Table 1 Statistics of doping components, effective field strength and emission cross section of erbium-doped silicate glass

[0038]

[0039]

[0040] Table 2 Er in erbium-doped silicate glass 3+ Statistics of coordination numbers between ions and secondary coordinated ions

[0041] Example 1#: (See Table 1 and Table 2, Figure 1 and Figure 2 )

[0042] The molar composition of the silicate glass of this embodiment is: SiO2: 79.2mol%, Na2O: 20mol%, Er2O3: 0.8mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 1 hour during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 450°C. After keeping warm for 3 hours, it is cooled to room temperature with the furnace to obtain Example 1# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 1 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 2 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0043] Calculate the effective field strength of the silicate glass, where Na + The field strength of the ion is A1 = 0.19 × 10 -16 cm -2 , Er 3+ Ions and Na +The coordination number of the ion is B1 = 8.5, so the calculated effective field strength is E = 0.19 × 10 -16 cm -2 .

[0044] Example 2#: (See Table 1 and Table 2, Figure 1 and Figure 2 )

[0045] The molar composition of the silicate glass of this embodiment is: SiO2: 59.2mol%, Na2O: 40mol%, Er2O3: 0.8mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 1 hour during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 450°C. After keeping warm for 3 hours, it is cooled to room temperature with the furnace to obtain Example 2# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 1 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 2 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0046] The effective field strength of the silicate glass is calculated to be E = 0.19 × 10 -16 cm -2 .

[0047] Example 3#: (See Table 1 and Table 2, Figure 1 and Figure 2 )

[0048] The molar composition of the silicate glass of this embodiment is: SiO2: 37.0mol%, Na2O: 60mol%, Er2O3: 3.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 1 hour during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 450°C. After keeping warm for 3 hours, it is cooled to room temperature with the furnace to obtain Example 3# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 1 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 2 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0049] The effective field strength of the silicate glass is calculated to be E = 0.19 × 10 -16 cm -2 .

[0050] Example 4#: (See Table 1 and Table 2, Figure 3 and Figure 4 )

[0051] The molar composition of the silicate glass of this embodiment is: SiO2: 79.2mol%, Li2O: 20mol%, Er2O3: 0.8mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 2 hours during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 450°C. After keeping warm for 4 hours, it is cooled to room temperature with the furnace to obtain Example 4# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 3 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 4 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0052] The effective field strength of the silicate glass is calculated to be E = 0.23 × 10 -16 cm -2 .

[0053] Example 5#: (See Table 1 and Table 2, Figure 3 and Figure 4 )

[0054] The molar composition of the silicate glass of this embodiment is: SiO2: 59.2mol%, Li2O: 40mol%, Er2O3: 0.8mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 2h during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 450°C. After keeping warm for 4h, it is cooled to room temperature with the furnace to obtain Example 5# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 3 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 4 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0055] The effective field strength of the silicate glass is calculated to be E = 0.23 × 10 -16 cm -2 .

[0056] Example 6#: (See Table 1 and Table 2, Figure 3 and Figure 4 )

[0057] The molar composition of the silicate glass of this embodiment is: SiO2: 39.9mol%, Li2O: 40mol%, Er2O3: 0.1mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 2 hours during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 450°C. After keeping warm for 4 hours, it is cooled to room temperature with the furnace to obtain Example 6# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 3 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 4 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0058] The effective field strength of the silicate glass is calculated to be E = 0.23 × 10 -16 cm -2 .

[0059] Example 7#: (See Table 1 and Table 2, Figure 5 , Figure 6 , Fig.10 and Fig.11 )

[0060] The molar composition of the silicate glass of this embodiment is: SiO2: 59mol%, MgO: 10mol%, Na2O: 30mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1300°C, continuously introducing oxygen for 3 hours during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 485°C. After keeping warm for 5 hours, it is cooled to room temperature with the furnace to obtain Example 7# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 5 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 6 The emission cross section is calculated by molecular dynamics simulation. 3+The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0061] The effective field strength of the silicate glass is calculated to be E = 0.21 × 10 -16 cm -2 The glass #7 of Example 7 was prepared into a preform rod, drawn into an erbium-doped silicate optical fiber, and its ASE was tested. Fig.10 As shown, the test obtains the gain of L band, such as Fig.11 shown.

[0062] Example 8#: (See Table 1 and Table 2, Figure 5 and Figure 6 )

[0063] The molar composition of the silicate glass of this embodiment is: SiO2: 59mol%, MgO: 15mol%, Na2O: 25mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1300°C, continuously introducing oxygen for 3 hours during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 485°C. After keeping warm for 5 hours, it is cooled to room temperature with the furnace to obtain Example 8# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 5 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 6 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0064] The effective field strength of the silicate glass is calculated to be E = 0.23 × 10 -16 cm -2 .

[0065] Example 9#: (See Table 1 and Table 2, Figure 5 and Figure 6 )

[0066] The molar composition of the silicate glass of this embodiment is: SiO2: 59mol%, MgO: 20mol%, Na2O: 20mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1350°C, continuously introducing oxygen for 3 hours during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 520°C. After keeping warm for 5 hours, it is cooled to room temperature with the furnace to obtain Example 9# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 5 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 6 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0067] The effective field strength of the silicate glass is calculated to be E = 0.26 × 10 -16 cm -2 .

[0068] Example 10#: (See Table 1 and Table 2, Figure 5 and Figure 6 )

[0069] The molar composition of the silicate glass of this embodiment is: SiO2: 59mol%, MgO: 22.5mol%, Na2O: 17.5mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1400℃, continuously introducing oxygen for 3h during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 560℃. After keeping warm for 5h, it is cooled to room temperature with the furnace to obtain Example 10# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 5 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 6 The emission cross section is calculated by molecular dynamics simulation. 3+The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0070] The effective field strength of the silicate glass is calculated to be E = 0.27 × 10 -16 cm -2 .

[0071] Example 11#: (See Table 1 and Table 2, Figure 5 , Figure 6 , Fig.10 and Fig.11 )

[0072] The molar composition of the silicate glass of this embodiment is: SiO2: 59mol%, MgO: 25mol%, Na2O: 15mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, placing the mixed glass batch into a crucible, melting at 1400℃, continuously introducing oxygen for 3h during the melting process to remove water, pouring the molten glass into a preheated iron mold to form, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 560℃. After keeping warm for 5h, it is cooled to room temperature with the furnace to obtain Example 11# glass. The glass sheet polished to 1mm is tested for its fluorescence spectrum using a 980nm laser. The test range is 1425-1650nm. Figure 5 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 6 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0073] The effective field strength of the silicate glass is calculated to be E = 0.29 × 10 -16 cm -2 The glass of Example 11# was used to prepare a preform rod, which was drawn into an erbium-doped silicate optical fiber, and its ASE was tested. Fig.10 As shown, the test obtains the gain of L band, such as Fig.11 shown.

[0074] Example 12#: (See Table 1 and Table 2, Figure 7 and Figure 8 )

[0075] The molar composition of the silicate glass of this embodiment is: SiO2: 44mol%, Al2O3: 2mol%, Y2O3: 13mol%, La2O3: 8mol%, SrO: 8mol%, BaO: 9mol%, Na2O: 5mol%, K2O: 10mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, charging the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 2h during the melting process to remove water, pouring the molten glass into a preheated iron mold for forming, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 550°C. After keeping warm for 5h, it is cooled to room temperature with the furnace to obtain the glass of embodiment 12#. After polishing the glass sheet to 1mm, use a 980nm laser to test its fluorescence spectrum. The test range is 1425-1650nm. Figure 7 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 8 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0076] The effective field strength of the silicate glass is calculated to be E = 0.20 × 10 -16 cm -2 .

[0077] Example 13#: (See Table 1 and Table 2, Figure 7 and Figure 8 )

[0078] The molar composition of the silicate glass of this embodiment is: SiO2: 44mol%, Al2O3: 7mol%, Y2O3: 8mol%, La2O3: 10mol%, CaO: 8mol%, SrO: 7mol%, Na2O: 9mol%, K2O: 6mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing the raw materials, fully mixing to form 200g of glass batch, charging the mixed glass batch into a crucible, melting at 1450°C, continuously introducing oxygen for 2h during the melting process to remove water, pouring the molten glass into a preheated iron mold for forming, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 550°C. After keeping warm for 5h, it is cooled to room temperature with the furnace to obtain Example 13# glass. After polishing the glass sheet to 1mm, use a 980nm laser to test its fluorescence spectrum. The test range is 1425-1650nm. Figure 7As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 8 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0079] The effective field strength of the silicate glass is calculated to be E = 0.25 × 10 -16 cm -2 .

[0080] Example 14#: (See Table 1 and Table 2, Figure 7 and Figure 8 )

[0081] The silicate glass of this embodiment has a molar composition of SiO2: 44 mol%, Al2O3: 10.5 mol%, Y2O3: 4.5 mol%, La2O3: 7.2 mol%, MgO: 8 mol%, SrO: 9.8 mol%, Li2O: 8.2 mol%, Na2O: 6.8 mol%, Er2O3: 1.0 mol%. The glass is prepared by direct firing method, and the preparation steps include: weighing raw materials, fully mixing to form 200 g of glass batch, charging the mixed glass batch into a crucible, melting at 1400° C., continuously introducing oxygen for 2 h during the melting process to remove water, pouring the melted glass into a preheated iron mold for molding, and finally putting it into an annealing furnace for annealing treatment. The annealing furnace temperature is 550° C., after keeping the temperature for 5 h, cooling to room temperature with the furnace, and obtaining the glass of embodiment 14#. After polishing to 1mm, the glass piece was tested for fluorescence spectrum using 980nm laser. The test range was 1425-1650nm. Figure 7 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 8 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper: The effective field strength of the silicate glass is calculated to be E = 0.31 × 10 -16 cm -2 .

[0082] Example 15#: (See Table 1 and Table 2, Figure 7 and Figure 8 )

[0083] The molar composition of the silicate glass of this embodiment is: SiO2: 44mol%, Al2O3: 12.5mol%, Y2O3: 2.5mol%, La2O3: 11.8mol%, MgO: 13.2mol%, Li2O: 9.6mol%, K2O: 5.4mol%, Er2O3: 1.0mol%. It is prepared by direct firing method, and the preparation steps include: weighing raw materials, fully mixing to form 200g glass batch, charging the mixed glass batch into a crucible, melting at 1400°C, continuously introducing oxygen for 2h to remove water during the melting process, pouring the melted glass into a preheated iron mold for molding, and finally putting it into an annealing furnace for annealing treatment, the annealing furnace temperature is 550°C, after keeping the temperature for 5h, cooling to room temperature with the furnace, and obtaining the embodiment 15# glass. After polishing to 1mm, the glass piece was tested for fluorescence spectrum using 980nm laser. The test range was 1425-1650nm. Figure 1 As shown in Table 1, the normalized fluorescence spectrum was plotted at 1535 nm. Figure 2 The emission cross section is calculated by molecular dynamics simulation. 3+ The coordination number of the ion and the second coordinated ion is shown in Table 2. According to the effective field strength calculation formula proposed in this paper:

[0084] The effective field strength of the silicate glass is calculated to be E = 0.35 × 10 -16 cm -2 .

[0085] As shown in Table 1, Figure 1 , 2 , 3, 4, Examples 1#, 2#, 3#, 4#, 5#, 6# show that changing Na + Ion or Li + Ion content, Er 3+ The emission spectra of ions remain unchanged and the emission cross sections are almost the same, while Li + Ion replacement Na + After ionization, Er 3+ The emission spectrum of the ion is broadened. 3+ The emission spectrum of Er in the L band has nothing to do with the content of alkali metals in silicate glass, but is related to the type of alkali metals. 3+ The second coordination ion of the ion is the network extracellular cation. The type of the second coordination ion affects Er 3+ The local structure and coordination environment of ions.

[0086] As shown in Table 1, Figure 5 , 6As shown, Examples 2#, 7#, 8#, 9#, 10#, and 11# show that Er 3+ The emission spectrum of ions in the L band varies with the high field strength of the network extracellular Mg 2+ The emission cross section at 1600nm increases with the increase of ions. Therefore, the higher the network external field strength in silicate glass, the 3+ The larger the emission cross section of the ion in the L band. Figure 7 , 8 As shown, in Examples 11#, 12#, 13#, 14#, and 15#, the rule that the higher the effective field strength of the glass, the larger the emission cross section is verified, and silicate glass with a high emission cross section in the L band is obtained.

[0087] As shown in Table 1 and Fig. 9 As shown, the effective field strength and emission cross section of all glasses in the embodiments are plotted as scatter plots. Embodiments 1#-15# show that the effective field strength E of the glass and the emission cross section σ e1600 The relationship formula satisfies: e1600 =-19.6+120E, where the coefficient of determination R 2 =92.6%.

[0088] like Fig.10 , 11 As shown, the silicate optical fibers prepared in Examples 7# and 10# show that the high-field network exosome improves the emission cross-section and optical fiber gain of Er-doped silicate optical fiber in the L-band, and is a practical optical fiber medium material for achieving high gain in the L-band. The optical fiber prepared in Example 10# achieves an amplification gain greater than 20 dB in the L-band.

[0089] Obviously, adding high-field network foreign bodies to silicate glass can increase Er 3+ The emission cross section of ions in the L-band is beneficial to expanding the gain bandwidth of Er-doped silicate optical fiber in the L-band.

[0090] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An erbium-doped silicate glass with enhanced L-band luminescence, characterized in that: The molar composition range of the silicate glass is SiO2: 44-79.2 mol%, Al2O3: 0-12.5 mol%, Y2O3: 0-13 mol%, La2O3: 0-11.8 mol%, MgO: 0-25 mol%, CaO: 0-8 mol%, SrO: 0-9.8 mol%, BaO: 0-9 mol%, Li2O: 0-60 mol%, Na2O: 0-60 mol%, K2O: 0-10 mol%, Er2O3: 0.1-3 mol%.

2. The L-band luminescence-enhanced erbium-doped silicate glass according to claim 1, characterized in that: The molar composition of the silicate glass is SiO2: 44 mol%, Al2O3: 12.5 mol%, Y2O3: 2.5 mol%, La2O3: 11.8 mol%, MgO: 13.2 mol%, CaO: 0 mol%, SrO: 0 mol%, BaO: 0 mol%, Li2O: 9.6 mol%, Na2O: 0 mol%, K2O: 5.4 mol%, Er2O3: 1.0 mol%.

3. The L-band luminescence-enhanced erbium-doped silicate glass according to claim 1, characterized in that: The molar composition of the silicate glass is SiO2: 44 mol%, Al2O3: 10.5 mol%, Y2O3: 4.5 mol%, La2O3: 7.2 mol%, MgO: 8 mol%, CaO: 0 mol%, SrO: 9.8 mol%, BaO: 0 mol%, Li2O: 8.2 mol%, Na2O: 6.8 mol%, K2O: 0 mol%, Er2O3: 1 mol%.

4. The L-band luminescence-enhanced erbium-doped silicate glass according to claim 1, characterized in that: The molar composition of the silicate glass is SiO2: 59 mol%, Al2O3: 0 mol%, Y2O3: 0 mol%, La2O3: 0 mol%, MgO: 25 mol%, CaO: 0 mol%, SrO: 0 mol%, BaO: 0 mol%, Li2O: 0 mol%, Na2O: 15 mol%, K2O: 0 mol%, Er2O3: 1.0 mol%.

5. The L-band luminescence-enhanced erbium-doped silicate glass according to claim 2, characterized in that: The effective field strength of the silicate glass is 0.35×10 -16 cm -2 The emission cross section at 1600nm wavelength reaches 23.5×10 -22 cm 2 .

6. The L-band luminescence-enhanced erbium-doped silicate glass according to claim 3, characterized in that: The effective field strength of the silicate glass is 0.31×10 -16 cm -2 The emission cross section at 1600nm wavelength reaches 19.1×10 -22 cm 2 .

7. The L-band luminescence-enhanced erbium-doped silicate glass according to claim 4, characterized in that: The effective field strength of the silicate glass is 0.29×10 -16 cm -2 , the emission cross section at 1600nm wavelength reaches 14.3×10 -22 cm 2 .

8. The L-band luminescence-enhanced erbium-doped silicate glass according to claim 1, characterized in that: The effective field strength (E) and emission cross section (σ e1600 ) is: e1600 =-19.6+120E, where the coefficient of determination R 2 =92.6%, the effective field strength E is obtained by the following formula: Where i is the type of network extracellular cation in the glass, B represents the coordination number between Er3+ ions and the second coordination ions in the glass calculated by molecular dynamics simulation, and A is the field strength of the network extracellular cation in the glass, which is obtained by dividing the valence state of the cation by the square of the distance between the cation and oxygen.

9. An optical fiber made of erbium-doped silicate glass with enhanced L-band luminescence according to claim 1, characterized in that: The optical fiber can obtain a gain greater than 20 dB in the L band.

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