Dysprosium-doped quartz glass with enhanced visible light emission and method for producing the same

Abstract

The application discloses a dysprosium-doped quartz glass with enhanced visible light band emission and a preparation method thereof, and aims to solve the problems of small absorption coefficient and low light emission efficiency in the dysprosium-doped quartz glass. The molar composition of the quartz glass is as follows: Dy2O3: 0.03-0.3 mol%, Al2O3: 1-4 mol%, P2O3: 0-5 mol%, Ce2O3: 0-1 mol%, Tb2O3: 0-0.1 mol%, and SiO2: 93.7-98.97 mol%. The application greatly improves the light emission efficiency of the dysprosium-doped quartz glass in the visible light band by increasing the absorption coefficient, dredging the particle number of the light emission lower energy level and optimizing the local environment, and has the advantages of simple preparation method, low cost and the like, and can be used in the visible light band fiber laser, and has great promoting significance for the development of the fields of laser medical treatment, Einstein condensation and astronomy.

Description

Technical Field

[0001] This invention belongs to the field of optical fiber technology and relates to a dysprosium-doped quartz glass with enhanced light emission in the visible light band. Technical Background

[0002] Visible lasers have important applications in fields such as laser medicine, lidar, remote sensing, and national defense; in particular, yellow light (565-590nm) lasers have important applications in fields such as retinal photocoagulation therapy, astronomy (laser guide star), and Bose-Einstein condensation, so the demand for yellow light lasers has surged both domestically and internationally.

[0003] Most rare earth ions (such as Er) 3+ Yb 3+ Ho 3+ Tm 3+ Pr 3+ 、Nd 3+ The emission spectra of dysprosium ions (Dy) do not involve yellow light wavelengths; 3+ Because the main emission peak is located in the yellow light band (Dy 3+ : 4 F 9 / 2 → 4 H 13 / 2 This has become a research hotspot. Currently, Dy 3+ Fluoride-doped optical fibers can achieve continuous-wave laser output power of 1.12 W at a wavelength of yellow light (see Photonics Research. 2021; 9(4):446-451). However, fluoride optical fibers have disadvantages such as difficult raw material purification, high requirements for equipment and environment in the preparation process, poor mechanical properties, and unstable physicochemical properties, which not only increase the difficulty and cost of preparation, but also bring many uncontrollable factors to their practical application. In contrast, quartz optical fibers have greater practical application value due to their compact structure, high mechanical strength, stable physicochemical properties, and mature preparation process.

[0004] On the other hand, although Dy 3+ Ions in quartz glass optical fibers can achieve gain in the visible light band, but problems such as low absorption efficiency at the pump wavelength and weak fluorescence intensity limit the application of dysprosium-doped quartz glass in visible light lasers and other fields. Summary of the Invention

[0005] In order to overcome the shortcomings and difficulties of existing technologies, this invention provides a dysprosium-doped quartz glass with enhanced light emission in the visible light band and its preparation method.

[0006] This invention provides a dysprosium-doped quartz glass with enhanced luminescence in the visible light band, wherein the quartz glass contains dysprosium ions (Dy). 3+ ) and aluminum ions (Al3+ ) and co-doped silica glass, wherein the co-doped ions include P 5+ Ce 3+ 、Tb 3+ One or a combination of several.

[0007] The molar composition of the quartz glass is as follows: Dy2O3: 0.03-0.3 mol%, Al2O3: 1-4 mol%, P2O3: 0-5 mol%, Ce2O3: 0-1 mol%, Tb2O3: 0-0.1 mol%, SiO2: 93.7-98.97 mol%.

[0008] The dysprosium-doped quartz glass has a fluorescence lifetime of not less than 500 μs at the yellow light wavelength.

[0009] In a preferred embodiment, the Dy2O3 content of the quartz glass is not less than 0.06 mol%.

[0010] In another preferred embodiment, the Ce2O3 content of the quartz glass is no more than 0.5 mol%.

[0011] In another preferred embodiment, the Al2O3 content in the quartz glass is 2.5 mol%, 2.8 mol%, or 2.9 mol%.

[0012] A method for preparing dysprosium-doped quartz glass with enhanced visible light emission is a direct sintering method, or a sol-gel combined vacuum sintering method, or a modified chemical vapor deposition (MCVD) method.

[0013] Furthermore, the direct sintering method is as follows:

[0014] S1. Prepare the raw materials according to the following proportions: Dy2O3: 0.03-0.3 mol%, Al2O3: 1-4 mol%, P2O3: 0-5 mol%, Ce2O3: 0-1 mol%, Tb2O3: 0-0.1 mol%, SiO2: 93.7-98.97 mol%.

[0015] S2. Raw material mixing: Based on the molar ratio of each oxide in step S1, convert it into the corresponding mass parts, weigh the oxide raw materials, and mix them using a ball mill; the mixing time is 10 hours, and the ball mill speed is set to 50 r / min.

[0016] S3. The mixed raw materials are placed into a crucible and fired in a vacuum high-temperature furnace at 1750°C for 2 hours. The crucible is made of corundum.

[0017] S4. Annealing: the furnace is cooled to 1200°C and held for 0.5 hours, then cooled to room temperature to obtain the quartz glass.

[0018] Technical effects of the present invention:

[0019] 1. This invention utilizes P doping 5+ And Al 3+ Improving the dispersion of rare earth ions reduces clustering and enhances luminescence efficiency by utilizing Ce. 3+ Ions are used to increase the pump absorption coefficient of quartz glass in the ultraviolet-blue light band, utilizing Tb 3+ Ion matching energy levels 7 F4 to unclog Dy 3+ Energy levels of ions under visible light emission 4 H 13 / 2 The number of particles solved Dy 3+ This addresses the issues of low ion absorption coefficient and low luminous efficiency, thereby achieving the beneficial effect of significantly improving the absorption coefficient and luminous efficiency of dysprosium-doped quartz glass.

[0020] 2. The preparation method of the present invention is simple, reducing the difficulty and cost of glass manufacturing.

[0021] 3. The dysprosium-doped quartz glass of the present invention has the characteristics of high absorption efficiency of pump light and high luminous intensity in the visible light band. It can be used in fiber lasers in the visible light band, which has great significance for promoting the development of laser medicine, Einstein condensation, astronomy and other fields. Attached Figure Description

[0022] Figure 1 The absorption spectra of Examples 1# and 8# of the present invention are shown below;

[0023] Figure 2 These are fluorescence decay diagrams for Examples 1#, 3#, and 4# of the present invention;

[0024] Figure 3 The fluorescence lifetime at 576 nm for embodiments 1#, 3#, 4#, 8#, and 9# of the present invention;

[0025] Figure 4 The fluorescence spectra are those of Examples 1# and 9# of the present invention. Detailed Implementation

[0026] The present invention will be described in detail below with reference to embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.

[0027] Table 1 shows the doping composition and fluorescence intensity ratio in the visible light band of 10 embodiments of dysprosium-doped quartz glass with enhanced visible light luminescence.

[0028] Table 1. Statistics on doping composition and fluorescence intensity ratio of dysprosium-doped quartz glass.

[0029]

[0030] Example 1#: (See Table 1, Figure 1 , Figure 2 , Figure 3 and Figure 4 )

[0031] The molar composition of the quartz glass in this embodiment is: 0.03 mol% Dy₂O₃ - 1.0 mol% Al₂O₃ - 98.97 mol% SiO₂. The quartz glass is prepared using a direct firing method: 1) Raw material ball milling and mixing. The oxide raw materials are weighed according to the oxide ratio and converted to mass fractions. The mixture is then ball milled for 10 hours at 50 r / min using a planetary ball mill; 2) Vacuum firing. The mixed raw materials are placed in a corundum crucible and fired in a vacuum high-temperature furnace at 1750℃ for 2 hours; 3) Annealing. The furnace temperature is lowered to 1200℃ and held for 0.5 hours, then lowered to room temperature. The quartz glass is obtained. The glass is processed into 1 mm glass sheets, polished on both sides, and the absorption spectrum (e.g., ...) is tested. Figure 1 As shown), a xenon lamp at 350 nm was used as the pump source to test the fluorescence spectrum of the glass slide (as shown). Figure 4 As shown), the spontaneous emission intensity in the wavelength range of 420–650 nm was collected; and the fluorescence lifetime curve at 576 nm was measured (as shown). Figure 2 As shown), the fluorescence lifetime (as shown) was obtained by exponential fitting. Figure 3 (As shown in Table 1). To compare the effect of the component design of the present invention, the fluorescence intensity of Example 1# at 480nm and 576nm was set to 100% of the standard value, as shown in Table 1.

[0032] Example 2#: (See Table 1)

[0033] The molar composition of the quartz glass in this embodiment is: 0.06 mol% Dy₂O₃ - 1.5 mol% Al₂O₃ - 98.44 mol% SiO₂. The quartz glass was prepared using a direct firing method. The process involved weighing the raw materials, ball milling and mixing them, vacuum firing, and annealing to obtain the quartz glass. The glass was then processed into a 1 mm thick glass sheet, polished on both sides, and its absorption spectrum was tested. A 350 nm xenon lamp was used as the pump light source to test the fluorescence spectrum of the glass sheet, collecting the spontaneous emission intensity in the wavelength range of 420–650 nm. The fluorescence lifetime curve at 576 nm was also tested, and the fluorescence lifetime was obtained using exponential fitting. The ratios of the fluorescence intensity at 480 nm and 576 nm to that of Example 1# are shown in Table 1, which are 155% and 179%, respectively.

[0034] Example 3#: (See Table 1, Figure 2 and Figure 3 )

[0035] The molar composition of the quartz glass in this embodiment is: 0.06 mol% Dy₂O₃ - 1.0 mol% P₂O₃ - 2.59 mol% Al₂O₃ - 96.35 mol% SiO₂. The quartz glass is prepared using a direct firing method. This involves weighing the raw materials, ball milling and mixing them, vacuum firing, and annealing to obtain the quartz glass. The glass is then processed into a 1 mm thick glass sheet, polished on both sides, and its absorption spectrum is tested. A 350 nm xenon lamp is used as the pump light source to test the fluorescence spectrum of the glass sheet. The spontaneous emission intensity in the wavelength range of 420–650 nm is collected. The fluorescence lifetime curve at 576 nm is also tested (e.g., ...). Figure 2 As shown), the fluorescence lifetime (as shown) was obtained by exponential fitting. Figure 3 (As shown). The ratios of its fluorescence intensity at 480 nm and 576 nm to that of Example 1# are shown in Table 1, which are 224% and 230%, respectively.

[0036] Example 4#: (See Table 1, Figure 2 and Figure 3 )

[0037] The molar composition of the quartz glass in this embodiment is: 0.14 mol% Dy₂O₃ - 1.06 mol% P₂O₃ - 4 mol% Al₂O₃ - 94.8 mol% SiO₂. The quartz glass is prepared using a direct firing method. This involves weighing the raw materials, ball milling and mixing them, vacuum firing, and annealing to obtain the quartz glass. The glass is then processed into a 1 mm thick glass sheet, polished on both sides, and its absorption spectrum is tested. A 350 nm xenon lamp is used as the pump light source to test the fluorescence spectrum of the glass sheet. The spontaneous emission intensity in the wavelength range of 420–650 nm is collected. The fluorescence lifetime curve at 576 nm is also tested (e.g., ...). Figure 2 As shown), the fluorescence lifetime (as shown) was obtained by exponential fitting. Figure 3(As shown in Table 1). The ratios of its fluorescence intensity at 480 nm and 576 nm to that of Example 1# are 397% and 409%, respectively.

[0038] Example 5#: (See Table 1)

[0039] The molar composition of the quartz glass in this embodiment is: 0.3 mol% Dy₂O₃ - 5 mol% P₂O₃ - 1 mol% Al₂O₃ - 93.7 mol% SiO₂. The quartz glass was prepared using a direct firing method. The process involved weighing the raw materials, ball milling and mixing them, vacuum firing, and annealing to obtain the quartz glass. The glass was then processed into a 1 mm thick glass sheet, polished on both sides, and its absorption spectrum was tested. A 350 nm xenon lamp was used as the pump light source to test the fluorescence spectrum of the glass sheet, collecting the spontaneous emission intensity in the wavelength range of 420–650 nm. The fluorescence lifetime curve at 576 nm was also tested, and the fluorescence lifetime was obtained using exponential fitting. The ratios of the fluorescence intensity at 480 nm and 576 nm to that of Example 1# are shown in Table 1, which are 889% and 911%, respectively.

[0040] Example 6#: (Table 1)

[0041] The molar composition of the quartz glass in this embodiment is: 0.06 mol% Dy₂O₃ - 1.2 mol% P₂O₃ - 2.63 mol% Al₂O₃ - 0.05 mol% Tb₂O₃ - 96.06 mol% SiO₂. The quartz glass was prepared using a direct firing method. The raw materials were weighed, ball-milled, mixed, vacuum-fired, and annealed to obtain the quartz glass. It was then processed into a 1 mm thick glass sheet, polished on both sides, and the absorption spectrum was tested. A 350 nm xenon lamp was used as the pump light source to test the fluorescence spectrum of the glass sheet, collecting the spontaneous emission intensity in the wavelength range of 420–650 nm. The fluorescence lifetime curve at 576 nm was also tested, and the fluorescence lifetime was obtained using exponential fitting. The ratios of the fluorescence intensity at 480 nm and 576 nm to that of Example 1# are shown in Table 1, which are 659% and 599%, respectively.

[0042] Example 7#: (See Table 1)

[0043] The molar composition of the quartz glass in this embodiment is: 0.06 mol% Dy₂O₃ - 1.15 mol% P₂O₃ - 2.38 mol% Al₂O₃ - 0.1 mol% Tb₂O₃ - 96.31 mol% SiO₂. The quartz glass was prepared using a direct firing method. The raw materials were weighed, ball-milled, mixed, vacuum-fired, and annealed to obtain the quartz glass. The glass was then processed into a 1 mm thick glass sheet, polished on both sides, and its absorption spectrum was tested. A 350 nm xenon lamp was used as the pump light source to test the fluorescence spectrum of the glass sheet, collecting the spontaneous emission intensity in the wavelength range of 420–650 nm. The fluorescence lifetime curve at 576 nm was also tested, and the fluorescence lifetime was obtained using exponential fitting. The ratios of the fluorescence intensity at 480 nm and 576 nm to that of Example 1# are shown in Table 1, which are 468% and 431%, respectively.

[0044] Example 8#: (See Table 1, Figure 1 and Figure 3 )

[0045] The molar composition of the quartz glass in this embodiment is: 0.06 mol% Dy₂O₃ - 1.6 mol% P₂O₃ - 2.5 mol% Al₂O₃ - 0.1 mol% CeO₂ - 95.74 mol% SiO₂. The quartz glass is prepared using a direct firing method, which involves weighing the raw materials, ball milling and mixing them, vacuum firing, and annealing to obtain the quartz glass. It is then processed into a 1 mm thick glass sheet, polished on both sides, and its absorption spectrum (e.g., ...) is tested. Figure 1 As shown), a xenon lamp at 350 nm was used as the pump source to test the fluorescence spectrum of the glass slide, collecting the spontaneous emission intensity in the wavelength range of 420–650 nm; and the fluorescence lifetime curve at 576 nm was measured. The fluorescence lifetime was obtained using exponential fitting (as shown). Figure 3 (As shown). The ratios of its fluorescence intensity at 480 nm and 576 nm to that of Example 1# are shown in Table 1, which are 4222% and 779%, respectively.

[0046] Example 9#: (See Table 1, Figure 1 , Figure 3 and Figure 4 )

[0047] The molar composition of the quartz glass in this embodiment is: 0.06 mol% Dy₂O₃ - 2 mol% P₂O₃ - 2.8 mol% Al₂O₃ - 0.5 mol% CeO₂ - 0.03 mol% Tb₂O₃ - 94.61 mol% SiO₂. The quartz glass is prepared using a direct firing method, involving raw material weighing, ball milling and mixing, vacuum firing, and annealing. The resulting quartz glass is then processed into 1 mm thick glass sheets, polished on both sides, and its absorption spectrum (e.g., ...) is tested. Figure 1As shown), a xenon lamp at 350 nm was used as the pump source to test the fluorescence spectrum of the glass slide, and the spontaneous emission intensity in the wavelength range of 420–650 nm was collected (e.g., as shown). Figure 4 (as shown); and the fluorescence lifetime curve at 576 nm was tested, and the fluorescence lifetime was obtained by exponential fitting (as shown). Figure 3 (As shown in Table 1). The ratios of its fluorescence intensity at 480 nm and 576 nm to that of Example 1# are 5179% and 868%, respectively.

[0048] Example 10#: (See Table 1)

[0049] The molar composition of the quartz glass in this embodiment is: 0.06 mol% Dy₂O₃ - 1.8 mol% P₂O₃ - 2.9 mol% Al₂O₃ - 1 mol% CeO₂ - 0.04 mol% Tb₂O₃ - 94.2 mol% SiO₂. The quartz glass was prepared using a direct firing method. The raw materials were weighed, ball-milled, mixed, vacuum-fired, and annealed to obtain the quartz glass. It was then processed into a 1 mm thick glass sheet, polished on both sides, and the absorption spectrum was tested. A 350 nm xenon lamp was used as the pump light source to test the fluorescence spectrum of the glass sheet, collecting the spontaneous emission intensity in the wavelength range of 420–650 nm. The fluorescence lifetime curve at 576 nm was also tested, and the fluorescence lifetime was obtained using exponential fitting. The ratios of the fluorescence intensity at 480 nm and 576 nm to that of Example 1# are shown in Table 1, which are 3750% and 748%, respectively.

[0050] Examples 2# to 3# show (as shown in Table 1) that P ions and Al ions can improve the dispersion of rare earth ions in the quartz glass grid and increase Dy 3+ The luminescence intensity, wherein the relative fluorescence intensity at 576 nm increased from 155% in Example 2# to 230% in Example 3#.

[0051] Examples 1#, 3#, and 4# show (as shown in Table 1, ...) Figure 2 and Figure 3 As shown), Dy 3+ The fluorescence lifetime of the ions decreased with increasing Dy concentration, from 641 μs in Example 1# to 514 μs in Example 4#. This is because Dy 3+ Due to the cross-relaxation effect between ions, the Dy concentration in quartz glass cannot be too high. To address this issue, this invention employs co-doping with Ce and Tb ions to significantly improve the luminescence intensity of Dy ions in the visible light band while ensuring a high fluorescence lifetime, and provides a suitable concentration ratio.

[0052] Example 1# and Example 8# (e.g.) Figure 1As shown in the figure, co-doping Ce in Dy-doped quartz glass can significantly improve its absorption coefficient for pump light, with the absorption coefficient at 350 nm increasing from 0.0326 cm⁻¹ in Example 1#. -1 Increased to 10.4cm in Example 8# -1 .

[0053] Examples 3#, 6#, 7#, 8#, and 9# show (Table 1) that, with Dy doping... 3+ Tb-doped quartz glass 3+ Effectively dredges Dy 3 + The lower energy level of the yellow light emission of ions can improve its luminescence efficiency, but Tb 3+ Excessive concentration will produce Dy 3+ To Tb 3+ The reverse energy transfer, therefore the appropriate Tb 3+ Concentration is very important.

[0054] Figure 4 This demonstrates the technical effect of the Dy-doped quartz glass composition design of the present invention, wherein the luminescence in the visible light band is significantly enhanced.

[0055] Obviously, Ce 3+ 、Tb 3+ The beneficial effects of the combined action of the ions are far greater than the results of doping each of the two ions individually.

[0056] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A dysprosium-doped quartz glass having enhanced emission in the visible wavelength band, characterized in that The quartz glass is a silica glass containing Dy 3+ and Al 3+ and co-doped with Tb 3+ , and the molar composition of the quartz glass ranges from Dy203: 0.06 to 0.3 mol%, Al203: 1 to 4 mol%, P203: 0 to 5 mol%, Ce203: 0 to 1 mol%, Tb203: 0.03 to 0.1 mol%, and Si02: 93.7 to 98.44 mol%.

2. The dysprosium-doped quartz glass of claim 1, wherein, The molar composition of the quartz glass is Dy2O3: 0.06mol%, Al2O3: 2.8mol%, P2O3: 2mol%, Ce2O3: 0.5mol%, Tb2O3: 0.03mol%, SiO2: 94.61mol%.

3. The dysprosium-doped quartz glass of claim 1, wherein, The molar composition of the quartz glass is Dy2O3: 0.06mol%, Al2O3: 2.9mol%, P2O3: 1.8mol%, Ce2O3: 1mol%, Tb2O3: 0.04mol%, SiO2: 94.2mol%.

4. The dysprosia-doped quartz glass of claim 1, wherein, The co-doping ions include Ce 3+ ions, the content of Ce203 in the quartz glass being greater than 0-0.5 mol%.

5. The dysprosium-doped quartz glass of claim 1, wherein, The quartz glass is applied to an optical fiber laser, and the co-doped ions include Ce 3+ ions, Tb 3+ ions.

6. A method of making a dysprosium-doped quartz glass having enhanced visible light band emission, the method comprising: providing a quartz glass; and doping the quartz glass with dysprosium. The molar composition according to any one of claims 1-5, wherein the quartz glass is prepared by direct melting method, sol-gel combined with vacuum sintering method or modified chemical vapor deposition method (MCVD).

7. Use of the Dy-doped quartz glass according to any one of claims 1-5 in yellow wavelength fiber laser.

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