Wideband high-transmittance perfluoride multiphase glass and preparation method thereof

Abstract

The invention discloses novel wide-band high-transmittance perfluoride complex-phase glass and a preparation method thereof. The novel wide-band high-transmittance perfluoride complex-phase glass specifically comprises the following components: 30 to 40 mol percent of AlF3, 28 to 30 mol percent of ZnF2, 11 to 27 mol percent of BaF2 + SrF2, 0 to 7 mol percent of CaF2 + MgF2 and 10 to 15 mol percent of YF3. The innovation of the invention lies in that the trigonal system AlF3 rhombohedral crystal is directionally separated out through component regulation and control, the crystal with the same component as the network former of the glass matrix is separated out in the perfluoride glass system for the first time, scattering caused by the refractive index difference between the crystal and the glass matrix is weakened, and the high-transmittance spectral range of the material is widened; and meanwhile, high spectrum flatness is realized. The wide-band high-transmittance fluoride complex-phase glass can realize full-band transmittance from 0.23 [mu] m to 7.2 [mu] m, and the transmittance is greater than or equal to 60%, wherein the transmittance of 0.86 [mu] m to 6.3 [mu] m is greater than or equal to 80%. The material is obtained through one step of melting and quenching, the preparation process is economical, simple and safe, and follow-up heat treatment is not needed.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of material preparation, in particular to a wide-band high-transmittance perfluoride composite glass and a preparation method thereof. BACKGROUND

[0002] Composite glass (glass-ceramics) is a new type of material composed of glass phase and crystal phase. By controlling the structure, composition and proportion of the two phases, unique characteristics can be exhibited. Fluoride glass is the only glass system known to maintain excellent transmittance from ultraviolet (200 nm) to mid-infrared (10 μm) range, and has potential applications in medical surgery, industry, remote sensing and national defense. However, fluoride glass lacks traditional glass network formers, and its poor thermal stability often leads to uncontrollable crystallization of glass, resulting in reduced transmittance of the material and narrowed high-transmittance wavelength range, which greatly hinders the development and wide application of fluoride composite glass.

[0003] AlF3-based glass is the fluoride glass family with the highest glass softening temperature and excellent environmental stability, which has advantages in high-temperature and humid application scenarios. However, there are few patents on AlF3-based perfluoride composite glass. In other fluoride glass systems, patent (CN117964242A) realizes the precipitation of ZnF2 single crystal in fluorozinc aluminum-based glass through heat treatment, but the glass-ceramic has a transmittance of less than 20% in the 0.2-1 μm wavelength range, and an average transmittance of not higher than 80% in the mid-infrared wavelength range, with poor flatness of the transmittance spectrum, which cannot meet the requirements of high transmittance for laser windows, and the subsequent heat treatment also increases the complexity and energy consumption of the process; patent (CN115650590A) realizes the precipitation of YF3 single crystal in fluorine indium-based glass through strong quenching, and the sample has a transmittance of less than 60% in the 0.2-1 μm wavelength range, with poor spectral flatness from visible to mid-infrared full wavelength range, which is difficult to meet the requirements of wide-band application scenarios. Patent (CN116768481A) discloses a ZrF4-based glass-ceramic containing ErF3 crystal phase, but the sample is opaque. It can be seen that the existing technology has reduced (partial wavelength) or even lost transmittance due to the mismatch of refractive index between the precipitated crystal and the glass matrix or the high crystallinity of the glass, which greatly hinders the application and development of the material in the fields of windows, imaging, etc. Therefore, there is an urgent need for a new perfluoride composite glass material with wide-band high transmittance. SUMMARY

[0004] The present application aims to provide a wide-band high-transmittance perfluoride composite glass with wide-band high transmittance and a preparation method thereof. This composite glass is different from the materials reported in the prior art: the precipitated crystal phase is consistent with the network former component of the glass matrix, which greatly reduces the transmittance loss caused by the mismatch of refractive index.

[0005] The technical solution of the present application is as follows:

[0006] The present application provides a wide-band high-transparency perfluoride composite glass, which comprises the following components in terms of mole percentage: AlF3: 30-40 mol%, ZnF2: 28-30 mol%, BaF2+SrF2: 11-27 mol%, MgF2+CaF2: 0-7 mol%, and YF3: 10-15 mol%. The microstructure of the composite glass comprises rhombohedral AlF3 crystals in trigonal system, and the composite glass is transparent in the full wave band of 0.23-7.2 μm with a transmittance of ≥60%, wherein the transmittance in the wave band of 0.86-6.3 μm is ≥80%. The wide-band high-transparency perfluoride composite glass is prepared by one-step melt quenching without any subsequent treatment.

[0007] Further, the mole ratio of BaF2 to SrF2 is (0-1.2):1.

[0008] Further, the mole ratio of MgF2 to CaF2 is (0-4):(0-5).

[0009] Further, the composite glass comprises the following components in terms of mole percentage: AlF3: 33-36 mol%, ZnF2: 28-30 mol%, BaF2+SrF2: 22-26 mol%, MgF2+CaF2: 0-7 mol%, and YF3: 11-13 mol%.

[0010] The present application also provides a preparation method of the wide-band high-transparency perfluoride composite glass, which comprises the following steps:

[0011] S1. Raw material preparation: the raw materials are weighed according to the component mole percentage of the wide-band high-transparency perfluoride composite glass and fully mixed;

[0012] S2. Melting: the mixed material is transferred to a platinum-rhodium crucible in a glove box with controllable atmosphere, and the crucible is placed in a muffle furnace with a furnace temperature of 1000-1050 ℃, and a glass melt is obtained after high-temperature melting for 20-30 minutes;

[0013] S3. Casting: the glass melt is directly cast into a mold preheated to 290±5 ℃, and naturally cooled to room temperature to obtain the wide-band high-transparency perfluoride composite glass containing rhombohedral AlF3 crystals in trigonal system.

[0014] Further, the method does not comprise any subsequent heat treatment step.

[0015] Further, the atmosphere in step S2 is high-purity dry nitrogen or argon.

[0016] Further, the material of the mold in step S3 is stainless steel or copper alloy.

[0017] The multiphase glass prepared by the method of the present invention is transparent across the entire wavelength range from 0.23 μm to 7.2 μm with a transmittance of ≥60%, wherein the transmittance in the wavelength range of 0.86 μm to 6.3 μm is ≥80% and the transmitted spectrum has high flatness.

[0018] The perfluoride multiphase glass with wide-band high transmittance described in this invention can be applied to the field of optical devices, such as mid-ultraviolet lithography windows, broadband laser windows, or multi-band sensors.

[0019] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0020] This invention, through the design of fluoride system components, prepares a broadband, high-transmittance perfluoride multiphase glass, which, compared with existing technologies:

[0021] 1. Through system design, this invention achieves for the first time a multiphase glass containing trigonal AlF3 rhombohedral crystals in an AlF3-based perfluoride glass system;

[0022] 2. This invention obtains multiphase glass in one step through direct casting. The preparation steps are simple, economical, and have a short cycle, without the need for further heat treatment.

[0023] 3. Ordinary fluoride glass ceramics typically cannot achieve both short-wavelength and long-wavelength transmission. This invention, however, precisely matches the refractive index of the AlF3 rhombohedral crystal with the glass substrate, extending the transmission window range to 0.23–7.2 μm for the first time. The sample is transparent across the entire wavelength range from 0.23 μm to 7.2 μm with a transmittance ≥60%, and the transmittance from 0.86 μm to 6.3 μm is ≥80%, exhibiting high flatness in the transmission spectrum. Compared to existing technologies, this significantly improves transmittance in the ultraviolet band while maintaining high average transmittance in the mid-infrared band. This patent fills the gap in high transmittance of fluoride glass ceramics from deep ultraviolet (DUV) to mid-infrared (Mid-IR). The prepared perfluoride multiphase glass can be applied to ultraviolet-infrared integrated optical devices, such as mid-ultraviolet lithography windows, broadband laser windows, and multi-band sensors. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of XRD diffraction of the broadband high-transmittance perfluoride multiphase glass of the present invention.

[0025] Figure 2 (a) is a distribution diagram of the broadband high-transmittance perfluoride multiphase glass crystal of the present invention at 5x magnification. Figure 2 (b) is a distribution diagram of the perfluoride multiphase glass crystals of the present invention with wide-band high transmittance at 50x magnification.

[0026] Figure 3 This is the transmission spectrum of the broadband high-transmittance perfluoride multiphase glass of the present invention. Detailed Implementation

[0027] The following specific embodiments are provided to illustrate the present invention and help to further understand the present invention. However, the specific details of the embodiments are only for illustrating the present invention and do not represent all the technical solutions under the concept of the present invention. Therefore, they should not be construed as limiting the overall technical solution of the present invention. Some non-substantial additions and modifications that do not deviate from the concept of the present invention in the view of those skilled in the art, such as simple substitution or replacement of technical features with the same or similar technical effects, are all within the protection scope of the present invention.

[0028] Example 1

[0029] In a glove box environment, 30g of raw material was weighed according to the molar percentage of 35AlF3-30ZnF2-11SrF2-11BaF2-13YF3, mixed, and transferred to a platinum-rhodium crucible. The crucible was placed in a high-temperature furnace at 1000℃ and melted for 20 minutes to obtain a glass melt. The glass melt was then cast into a mold preheated to 290±5℃ and allowed to cool naturally to room temperature to obtain a perfluoride multiphase glass with wide-band high transmittance containing trigonal AlF3 rhombic crystals.

[0030] Example 2

[0031] In a glove box environment, 50g of raw material was weighed according to the molar percentage of 37AlF3-28ZnF2-10SrF2-10BaF2-5CaF2-10YF3, mixed, and transferred to a platinum-rhodium crucible. The crucible was placed in a high-temperature furnace at 1050℃ and melted for 30 minutes to obtain a glass melt. The glass melt was then cast into a mold preheated to 290±5℃ and allowed to cool naturally to room temperature to obtain a perfluoride multiphase glass with wide-band high transmittance containing trigonal AlF3 rhombic crystals.

[0032] Examples 3-7

[0033] The experimental steps of Examples 3 to 7 are the same as those of Examples 1 and 2, except that the parameter values ​​are different. For details of the parameters, please refer to Table 1.

[0034] Table 1. Parameter values ​​for each embodiment

[0035]

[0036] Figure 1 This is a schematic diagram of XRD diffraction of the broadband high-transmittance perfluoride multiphase glass of the present invention. The characteristic diffraction peaks of AlF3 can be seen in the figure, indicating that the crystals precipitated in the multiphase glass are trigonal AlF3 single crystals.

[0037] Figure 2(a) is a crystal distribution diagram of the broadband high-transmittance perfluoride multiphase glass of the present invention at 5x magnification. The diagram shows a uniform distribution of AlF3 microcrystals within the multiphase glass; Figure 2 (b) is a distribution diagram of the perfluoride multiphase glass crystals of the present invention with wide-band high transmittance at 50x magnification. The crystals are clearly rhombohedral in shape.

[0038] Figure 3 The image shows the transmission spectrum of the broadband high-transmittance perfluoride multiphase glass of the present invention. As can be seen from the figure, the material has a transmittance of ≥60% across the entire wavelength range from 0.23 μm to 7.2 μm, with a transmittance of ≥80% in the 0.86 μm to 6.3 μm band, and the transmission spectrum exhibits high flatness.

[0039] As can be seen from the above embodiments, a broadband high-transmittance perfluoride multiphase glass can be prepared in one step through component design. The presence of the crystalline phase does not cause serious transmission loss. The material has the characteristics of broadband high transmittance and high transmittance spectrum flatness, and can be applied to fields such as mid-ultraviolet lithography windows, broadband laser windows or multi-band sensors.

Claims

1. A broadband, high-transmittance perfluoride multiphase glass, characterized in that, The molar percentage of the components in the multiphase glass is: AlF3: 30-40 mol% ZnF2: 28–30 mol% BaF2+SrF2: 11~27mol%, MgF2+CaF2: 0~7mol%, YF3: 10–15 mol% The microstructure of the composite glass contains trigonal AlF3 rhombohedral crystals, and the composite glass is transparent across the entire wavelength range from 0.23 μm to 7.2 μm with a transmittance of ≥60%, of which the transmittance in the 0.86 μm to 6.3 μm wavelength range is ≥80%.

2. The broadband high-transmittance perfluoride multiphase glass as described in claim 1, characterized in that, The molar ratio of BaF2 to SrF2 is (0-1.2):

1.

3. The broadband high-transmittance perfluoride multiphase glass as described in claim 1, characterized in that, The molar ratio of MgF2 to CaF2 is (0-4):(0-5).

4. The broadband high-transmittance perfluoride multiphase glass as described in claim 1, characterized in that, The molar percentage of the components in the multiphase glass is: AlF3: 33–36 mol%, ZnF2: 28–30 mol% BaF2+SrF2: 22-26 mol%, MgF2+CaF2: 0~7mol%, YF3: 11-13 mol%.

5. A method for preparing a broadband high-transmittance perfluoride multiphase glass as described in any one of claims 1 to 4, characterized in that, Includes the following steps: S1. Raw material preparation: Weigh the raw materials according to the molar percentage of the components of the broadband high-transmittance perfluoride multiphase glass and mix them thoroughly; S2. Melting: In a glove box with controlled atmosphere, the mixture is transferred to a platinum-rhodium crucible, and the crucible is placed in a muffle furnace at a furnace temperature of 1000-1050℃. After high-temperature melting for 20-30 minutes, glass melt is obtained. S3. Casting: The glass melt is directly cast into a mold preheated to 290±5℃ and allowed to cool naturally to room temperature to obtain a perfluoride multiphase glass with wide-band high transmittance containing trigonal AlF3 rhombic crystals.

6. The method for preparing a broadband high-transmittance perfluoride multiphase glass as described in claim 5, characterized in that, The method does not include any subsequent heat treatment steps.

7. The method for preparing a broadband high-transmittance perfluoride multiphase glass as described in claim 5, characterized in that, The atmosphere described in step S2 is high-purity, dry nitrogen or argon.

8. The method for preparing a broadband high-transmittance perfluoride multiphase glass as described in claim 5, characterized in that, The mold described in step S3 is made of stainless steel or copper alloy.

9. The method for preparing a broadband high-transmittance perfluoride multiphase glass as described in claim 5, characterized in that, The multiphase glass prepared by the method is transparent across the entire wavelength range from 0.23 μm to 7.2 μm with a transmittance of ≥60%, of which the transmittance in the 0.86 μm to 6.3 μm wavelength range is ≥80% and the transmitted spectrum has high flatness.

10. An optical device, characterized in that, The optical device comprises a perfluoride multiphase glass according to any one of claims 1 to 4, wherein the optical device includes a mid-ultraviolet lithography window, a broadband laser window, or a multi-band sensor.

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