Environment-friendly chalcogenide glass material with excellent acousto-optic properties and application thereof

Abstract

The application discloses an environmentally-friendly chalcogenide glass material with excellent acousto-optic characteristics and application thereof. The chemical composition of the chalcogenide glass material is Ga x Sn y Se 100‑x‑y‑z Te z , wherein x, y and z are molar fractions of Ga, Sn and Te respectively, x = 5-10, y = 15-20, and z = 3-7. The chalcogenide glass material contains stable [GaTe n Se 4‑n ] and [SnTe n Se 4‑n ] tetrahedral structures in the micro-network structure. The value of n is 0, 1, 2, 3 or 4. The chalcogenide glass material can be applied to the acousto-optic field as an acousto-optic medium. The chalcogenide glass material has excellent comprehensive performance, remarkable environmental-friendly characteristics, low cost advantage, good mechanical processing performance and optical stability in a variable temperature environment, and provides an ideal material for low-cost and large-scale manufacturing of high-performance acousto-optic devices such as acousto-optic modulators and deflectors.

Description

Technical Field

[0001] This invention belongs to the field of acousto-optic materials, specifically relating to an environmentally friendly chalcogenide glass material with excellent acousto-optic properties and its applications. Background Technology

[0002] Acousto-optic devices are a class of optoelectronic devices that modulate the frequency, intensity, and phase of optical signals based on the acousto-optic effect. They are widely used in optical communication, lidar, and spectral analysis. Their core components mainly consist of a piezoelectric transducer and an acousto-optic medium. The choice of acousto-optic medium material has a crucial impact on the performance of acousto-optic devices.

[0003] With the rapid development of acousto-optic modulation technology, acousto-optic devices are moving towards higher power, lower power consumption, lower heat generation, wider bandwidth response, and miniaturization. However, currently commercially available acousto-optic crystal materials (such as TeO2) are limited by their quality factor. M 2 (only 34.5 × 10 at a wavelength of 1.06 µm) -18 s 3 The low transmittance ( / g) of infrared acousto-optic devices, narrow transmittance range, and difficulty in large-scale fabrication make it difficult to fully meet the development needs of mid- and far-infrared acousto-optic devices. Therefore, developing devices with high transmittance ( / g) is crucial. M 2. The development of novel acousto-optic media materials with wide infrared transmission range, excellent thermal stability, and ease of preparation has become a key issue that urgently needs to be addressed in this field.

[0004] Chalcogenide glasses have become a research hotspot in acousto-optic media materials due to their advantages such as high refractive index, ultra-wide infrared transmission range (0.5~25 µm), flexible compositional tunability, and ease of large-scale fabrication. However, traditional acousto-optic chalcogenide glasses (such as As₂S₃, As₂Se₃, Ge-Sb-Se, etc.) generally suffer from poor acousto-optic properties and contain toxic or heavy metal elements such as As and Sb, making it difficult to meet the development requirements of high-performance and environmentally friendly acousto-optic devices. In addition, the high cost of Ge raw materials also restricts the commercialization process of acousto-optic devices to some extent. Therefore, it is urgent to develop new acousto-optic chalcogenide glass materials with excellent acousto-optic properties and environmental friendliness. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide an environmentally friendly chalcogenide glass material with excellent acousto-optic properties and its application, which addresses the shortcomings of the prior art. The chalcogenide glass material has excellent comprehensive performance, significant environmental friendliness, low cost advantage, good machinability and optical stability in variable temperature environments, and provides an ideal material for the low-cost and large-scale manufacturing of acousto-optic devices such as high-performance acousto-optic modulators and deflectors.

[0006] The technical solution adopted by this invention to solve the above-mentioned technical problem is: an environmentally friendly chalcogenide glass material with excellent acoustic and optical properties, the chemical formula of which is Ga. x Sn y Se 100-x-y-z Te z Where x, y, and z are the mole fractions of Ga, Sn, and Te, respectively, x = 5~10, y = 15~20, and z = 3~7. The microstructure of this chalcogenide glass material contains a stable [GaTe] group. n Se 4-n ] and [SnTe n Se 4-n The structure is tetrahedral, and the value of n can be 0, 1, 2, 3 or 4.

[0007] This invention Ga x Sn y Se 100-x-y-z Te z Chalcogenide glass materials achieve an optimized balance between material performance and cost through the synergistic optimization of Ga, Sn, and Te compositions, exhibiting excellent overall performance and significant advantages in cost control and comprehensive efficiency in the field of acousto-optic materials. This chalcogenide glass material innovatively replaces the expensive germanium (Ge) in traditional infrared glasses with the more affordable metallic gallium (Ga) and tin (Sn). While significantly reducing raw material costs, the introduction of high atomic polarizability elements tin (Sn) and tellurium (Te) synergistically constructs a stable tetrahedral network framework with high polarizability. This not only significantly improves the material's refractive index but also facilitates reversible bond angle and bond length perturbations under applied stress / acoustic field. Thus, while maintaining material homogeneity, it significantly improves the acousto-optic quality factor and acousto-optic modulation efficiency, making it an ideal material for high-performance infrared acousto-optic devices. Furthermore, the introduction of gallium (Ga) effectively solves the problem of decreased thermal stability of the glass network caused by increased tellurium content, enhancing the cross-linking degree and thermal stability of the glass network, and giving the material excellent resistance to crystallization and machinability. This chalcogenide glass material can be prepared using a vacuum melting-quenching-annealing process, overcoming the technical bottlenecks of traditional acousto-optic single crystal materials, such as long growth cycle, complex preparation process, and low yield. It provides an ideal material for the low-cost, large-scale manufacturing of acousto-optic devices such as high-performance acousto-optic modulators and deflectors.

[0008] This invention Ga x Sn y Se 100-x-y-z Te zChalcogenide glass materials also offer significant advantages in terms of environmental friendliness and production safety. Through optimized composition design, this material completely eliminates the highly toxic arsenic (As) and harmful antimony (Sb) elements commonly found in traditional acousto-optical chalcogenide glasses. Its composition complies with stringent international environmental regulations such as EU RoHS and REACH, removing environmental barriers for the product to enter the international market. Furthermore, in actual production and subsequent processing (such as cutting, grinding, and polishing), this material avoids the generation of toxic dust and waste liquids containing arsenic or antimony from the source, significantly improving process safety and environmental friendliness.

[0009] Preferably, the acousto-optic quality factor of the chalcogenide glass material at a wavelength of 1.55 µm is [value missing]. M The range of 2 is (332.36~456.61)×10 -18 s 3 / g, refractive index n The value is 2.566~2.628. Compared to commercial As2S3 and Ge... 33 As 12 Se 55 Compared to glass, the chalcogenide glass material of this invention has an extremely high acousto-optic quality factor, which significantly improves the acousto-optic diffraction efficiency and acousto-optic modulation capability of the material.

[0010] Preferably, the thermo-optical coefficient d of the chalcogenide glass material is... n / dT is (53.21~73.35)×10 -6 / K, ultrasonic attenuation coefficient at a 10MHz ultrasonic frequency α The variation range is 4.12~6.28 dB / cm. The thermo-optical coefficient d of this material... n / dT remains at (53.21~73.35)×10 -6 The material exhibits stable optical performance over a wide temperature range ( / K), which is beneficial for reliable operation of devices in varying temperature environments. The ultrasonic attenuation coefficient of this material... α The lower acousto-optic quality factor results in less energy loss during sound wave propagation within the material, which is beneficial for stable operation of the device at high frequencies and for low insertion loss design. This invention achieves a high acousto-optic quality factor. M 2 with a lower ultrasonic attenuation coefficient α A good balance between these properties makes it suitable for high-performance acousto-optic modulators, deflectors, and other devices.

[0011] Preferably, the chalcogenide glass material has a full-transmittance infrared band covering 0.8–25 µm, with a maximum transmittance of 60–65%. This material, with its full-transmittance infrared band covering 0.8–25 µm, is suitable for mid- and far-infrared optical and optoelectronic systems. Maintaining a high transmittance level over a wide wavelength range is beneficial for efficient optical signal transmission and improved overall device optical efficiency, making it applicable to various infrared applications such as thermal imaging, infrared sensing, and laser modulation.

[0012] Preferably, the optical band gap of the chalcogenide glass material E opg The laser damage threshold is 1.06~1.32 eV. F th The range is 3.16~5.35 J / cm. 2 The material has a moderate optical bandgap, which facilitates a balance between low absorption and high transmittance in the infrared region. Its laser damage threshold is significantly higher than that of commercial glass, enabling it to withstand higher power laser irradiation and making it suitable for high-power acousto-optic devices.

[0013] The above-mentioned environmentally friendly chalcogenide glass materials with excellent acoustic and optical properties are used as acoustic and optical media in the field of acoustics and optics.

[0014] The aforementioned environmentally friendly chalcogenide glass material, exhibiting excellent acoustic and optical properties, possesses good glass-forming ability and resistance to crystallization. It can be prepared using the following melt-quench process, making it suitable for large-size, mass production. The preparation method includes the following steps: (1) Weigh Ga, Sn, Se, and Te with a purity of 5N according to their chemical formulas, mix them, place them in a quartz tube, and evacuate to a vacuum degree of 10. -4 Pa, and seal the quartz tube; (2) Place the quartz tube in a swing furnace and melt it at 850~980℃ for 12~15 hours, then cool it down to 500~650℃ for water quenching; (3) The quenched glass is annealed at 100~300℃ for 8~10 hours, and then cooled at a cooling rate of 2~8℃ / hour to obtain the chalcogenide glass material.

[0015] Preferably, in step (2), the melting temperature is 900~930℃ and the quenching temperature is 570~620℃.

[0016] Preferably, in step (3), the annealing temperature is 160~220℃, and after annealing, it is cooled at a cooling rate of 4~8℃ / hour.

[0017] Compared with the prior art, the present invention has the following advantages: 1. The chalcogenide glass material of this invention possesses excellent comprehensive properties, with an acousto-optic quality factor of 1.55 µm. M The range of 2 is (332.36~456.61)×10 -18 s 3 / g, thermo-optic coefficient d n / dT is (53.21~73.35)×10 -6 / K, the ultrasonic attenuation coefficient at a 10 MHz ultrasonic frequency α The variation range is 4.12~6.28 dB / cm. It has excellent acousto-optic integrated characteristics, with higher acousto-optic diffraction efficiency and acousto-optic modulation capability, which is conducive to the stable operation of the device at high frequency and the design of low insertion loss. It can be widely used in the acousto-optic field. 2. The chalcogenide glass material of this invention has significant environmentally friendly characteristics. In its composition design, it completely eliminates the highly toxic or harmful heavy metal elements such as arsenic and antimony commonly found in traditional acousto-optic chalcogenide glass. Its composition complies with strict international environmental protection regulations such as EU RoHS and REACH, eliminating environmental barriers for the product to enter the international market and eliminating the risk of pollution to the environment from the source, while effectively avoiding potential harm to human health. 3. The chalcogenide glass material of this invention has the advantage of low cost. According to current market prices, the cost of high-purity (5N) raw materials for 1 kg of this chalcogenide glass material is 776.6~874.3 yuan, which is currently the lowest cost for commercially available acousto-optic chalcogenide glass. 33 As 12 Se 55 The cost reduction was 13.2% to 15.6% of the cost during the same period, representing a cost reduction of up to 85%, which greatly enhanced the product's market competitiveness and industrialization potential. 4. The chalcogenide glass material of this invention has a suitable Vickers hardness (145.1~203.3 kg / mm²). 2 ) and stable thermo-optic coefficient d n / dT((53.21~73.35)×10 -6 / K), exhibiting good machinability and optical stability under varying temperature environments; 5. The chalcogenide glass material of this invention can be prepared by vacuum melting-quenching-annealing process, which overcomes the technical bottlenecks of long growth cycle, complex preparation process and low yield of traditional acousto-optic single crystal materials, and provides an ideal material for low-cost and large-scale manufacturing of acousto-optic devices such as high-performance acousto-optic modulators and deflectors. Attached Figure Description

[0018] Figure 1 The ultrasonic attenuation coefficients of samples in Examples 1-3 α and longitudinal wave speed V LSchematic diagram showing the change with Te content; Figure 2 The ultrasonic attenuation coefficients of samples in Examples 4-6 α and longitudinal wave speed V L Schematic diagram showing the change with Te content; Figure 3 The ultrasonic attenuation coefficients of samples in Examples 7-9 α and longitudinal wave speed V L Schematic diagram showing the change with Te content; Figure 4 The ultrasonic attenuation coefficients of samples in Examples 4, 7, and 10. α and longitudinal wave speed V L Schematic diagram showing the change with Ga content; Figure 5 The ultrasonic attenuation coefficients of samples from Examples 1-10 and Comparative Examples 1-5. α Acoustic and optical quality factors M 2. Relationship diagram; Figure 6 Infrared transmission spectra of samples from Examples 1-3; Figure 7 Infrared transmission spectra of samples from Examples 4-6; Figure 8 Infrared transmission spectra of samples from Examples 7-10; Figure 9 The thermo-optic coefficient d of samples 1-3 in Examples n Schematic diagram of / dT as a function of temperature; Figure 10 The thermo-optic coefficient d of samples in Examples 4-6 n Schematic diagram of / dT as a function of temperature; Figure 11 The thermo-optic coefficient d of samples in Examples 7-9 n Schematic diagram of / dT as a function of temperature; Figure 12 The diagram shows the five-dimensional relationship between the acoustic and optical properties of Examples 1-10 and Comparative Examples 1 and 2. Detailed Implementation

[0019] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0020] Ten examples and five comparative examples of the chalcogenide glass materials of the present invention were selected, wherein the chemical composition of the chalcogenide glass materials of Examples 1 to 10 is Ga5Sn. 15 Se 77 Te3, Ga5Sn 15 Se 75Te5, Ga5Sn 15 Se 73 Te7, Ga5Sn 20 Se 72 Te3, Ga5Sn 20 Se 70 Te5, Ga5Sn 20 Se 68 Te7, Ga 10 Sn 20 Se 67 Te3, Ga 10 Sn 20 Se 65 Te5, Ga 10 Sn 20 Se 63 Te7, Ga 15 Sn 20 Se 62 Te3; the chemical formulas of the chalcogenide glass materials in Comparative Examples 1-5 are As2S3, Ge 33 As 12 Se 55 、Ge 12 Sb 32 S 56 、Ge 20 Sn 10 Se 70 Ga 15 Sn 18 Se 67 The performance data of the following comparative examples 1-5 are from existing literature.

[0021] The preparation methods of the chalcogenide glass materials in Examples 1-10 include the following steps: (1) Weigh Ga, Sn, Se, and Te elemental raw materials with a purity of 5N according to their chemical formulas, mix them, and place them in a quartz tube with a diameter of 15 mm. Then, evacuate the tube to a vacuum degree of 10. -4 Pa, and sealed the quartz tube with an oxyhydrogen flame; (2) Place the quartz tube in a swing furnace and melt it at 850~980℃ for 12~15 hours. Then cool it down to 500~650℃, take the quartz tube out of the swing furnace, and quench the quartz tube with cold water until the surface of the glass melt separates from the inner wall of the quartz tube. (3) Place the quenched glass into a precision annealing furnace and anneal it at a temperature below the glass transition temperature (T). g Anneal at 5~10℃ for 8~10 hours, then slowly cool to room temperature at a cooling rate of 4~8℃ / hour to release the internal stress of the glass and remove the chalcogenide glass rod; (4) Cut the chalcogenide glass rod into two samples with a thickness of 2 mm and one sample with a thickness of 10 mm. Use sandpaper, polishing pad and polishing liquid to polish the two samples with a thickness of 2 mm on one side and the two samples with a thickness of 10 mm on both sides to obtain chalcogenide glass samples.

[0022] Different properties of the acousto-optic chalcogenide glass samples from Examples 1-10 were tested respectively: I. Acousto-optic properties testing: Acousto-optic properties include longitudinal wave velocity. V L Ultrasonic attenuation coefficient α and acoustic-optical quality factor M 2. The longitudinal wave velocity of the samples from Examples 1 to 10 was measured using the pulse-echo method and in accordance with GB / T 5266-2006 standard. V L and ultrasonic attenuation coefficient α The system transmits and receives pulse signals using a pulse transmitter and receiver and an ultrasonic probe with a center frequency of 10 MHz. The longitudinal wave velocity is calculated based on the time difference between adjacent primary and secondary peaks of the echo on the oscilloscope. V L The ultrasonic attenuation coefficient is measured by the amplitude difference between adjacent primary and secondary peaks of the echo on the oscilloscope. α The measurement results are as follows Figures 1-4 As shown.

[0023] Figures 1-3 The ultrasonic attenuation coefficients of samples from Examples 1-3, 4-6, and 7-9. α and longitudinal wave speed V L Schematic diagram showing the change with Te content. Figures 1-3 It is evident that, because the bond energy of the heteropolar bonds associated with Te is lower than that of the heteropolar bonds associated with Se, the decrease in the total bond energy within the glass weakens the degree of structural cross-linking, thus reducing the ultrasonic attenuation coefficient. α The longitudinal wave velocity increases with increasing Te content, ranging from 4.12 to 6.28 dB / cm. V L The value decreases with increasing Te content, and its range is 2.362 × 10⁻⁶. 5 ~2.119×10 5 cm / s.

[0024] Figure 4 The ultrasonic attenuation coefficients of samples in Examples 4, 7, and 10. α and longitudinal wave speed V L Schematic diagram showing the change with Ga content. Figure 4It is evident that the increased Ga content leads to a higher average coordination number in the glass, resulting in a more compact internal network structure and a higher ultrasonic attenuation coefficient. α The sound velocity decreased from 5.07 dB / cm to 4.12 dB / cm, and the sound velocity decreased from 2.218 × 10⁻⁶. 5 cm / s increased to 2.362 × 10 5 cm / s.

[0025] The acoustic-optical quality factors of the samples in Examples 1-10 and Comparative Examples 1-5 were calculated using formula (1). M 2. Required parameters include refractive index. n Photoelastic coefficient p 12 ,density ρ and longitudinal wave speed V L .

[0026] , Among these methods, the photoelastic coefficient of the chalcogenide glass sample at a wavelength of 1.55 µm was measured using the Mach-Zehnder interferometry and with reference to patent standard BS 7604-1-1992. p 12 .

[0027] Acousto-optic quality factor of samples in Examples 1-10 M The calculation results for 2 are shown in Table 1. As can be seen from Table 1, the acoustic-optical quality factors for Examples 1-3, 4-6, and 7-9 are... M The range of 2 is 332.36 × 10 -18 s 3 / g~456.61×10 -18 s 3 / g. Derived from acoustic-optical quality factor M From the calculation formula of 2, we can see that the acoustic-optical quality factor M The value of 2 is affected by the refractive index. n The sixth power of the effect is most significant, and it is also related to the photoelastic coefficient. p 12 ,density ρ and longitudinal sound speed V L Closely related. As the Te content increases, the refractive index... n The increase, and the fact that all values ​​are greater than 2.55, leads to an increase in the acoustic-optical quality factor. M 2 increases significantly, with the minimum value being much higher than As2S3 (186.5 × 10). -18 s 3 / g), Ge 33 As 12 Se 55 (233.7×10) -18 s3 Commercial chalcogenide glasses such as / g). When the Sn content remains constant, the refractive index increases with increasing Ga content. n Increase, but audio-visual quality factor M 2. On the contrary, the refractive index decreases, especially in the sample of Example 1. n The minimum is 2.566, while the acoustic-optical quality factor is... M 2 reached 417.55×10 -18 s 3 / g, the reason being its low longitudinal sound velocity V L low density ρ and high photoelastic coefficient p 12 Although refractive index n To a certain extent, it can dominate the acoustic and optical quality factors. M 2 changes, but longitudinal sound speed V L ,density ρ Photoelastic coefficient p 12 This also determines the sound and light quality factor. M The magnitude of 2. When the Ga content remains constant, the above trend also applies as the Sn content increases.

[0028] As can be seen from Table 1, although the refractive index n Increase the sound and light quality factor M 2 increases, but longitudinal sound speed V L ,density ρ The increase in acoustic-optical quality factor M 2 decreases, and the final refractive index decreases. n The degree of change cannot dominate the acoustic-optical quality factor M Increasing the value of 2 actually increases its acoustic-optical quality factor. M 2 decreases.

[0029] Table 1 shows the ultrasonic attenuation coefficients of samples from Examples 1-10 and Comparative Examples 1, 2, 4, and 5. α The measured values ​​are at an ultrasonic frequency of 10 MHz; the ultrasonic attenuation coefficient of sample 3 in Comparative Example 3. α Data are for an ultrasonic frequency of 25 MHz (cited from the literature).

[0030] Figure 5 The ultrasonic attenuation coefficients of samples from Examples 1-10 and Comparative Examples 1-5. α Acoustic and optical quality factors M 2. Relationship diagram. Figure 5 The triangle corresponds to Examples 1-5, the square corresponds to Examples 1-3, the circle corresponds to Examples 4-6, the hexagon corresponds to Examples 7-9, and the rhombus corresponds to Example 10.

[0031] Table 1: Mechanical properties and acousto-optic characteristics at λ=1.55 µm of samples from Examples 1-10 and Comparative Examples 1-5

[0032] II. Optical Property Testing: The near-infrared transmission spectra of the double-sided polished samples from Examples 1-10 were measured using an infrared spectrophotometer. The results are as follows: Figures 6-8 The infrared transmission spectrum is shown. (From...) Figures 6-8 As can be seen, the highest transmittance of samples in Examples 1-10 is 60-70%; through analysis of the near-infrared absorption spectra, using the Tauc formula... hν and α The relationship can be used to calculate the optical band gap of chalcogenide glass samples. E opg value: , in, α (λ) is the linear absorption coefficient at wavelength λ. B Let be the probability constant for electronic transitions. hυ Photon energy, optical band gap E opg The results showed a range of 1.06–1.32 eV, as shown in Table 2.

[0033] The refractive index of a single-sided polished sample in the range of 1.5–20 μm was measured using an infrared variable angle ellipsometry. n The measurement results are shown in Table 1. For samples from Examples 1-3, 4-6, and 7-9, the Te content increased and the Se content decreased in the order of Examples 1-3, 4-6, and 7-9. Since Te has a higher atomic mass and polarizability than Se, the refractive index increased significantly as the Te content increased and the Se content decreased. For samples from Examples 1, 4, 7, and 10, with the increase of Ga content and the change of Sn content, the crosslinking density of the high polarizability (Sn) and high coordination tetrahedral (Ga, Sn) unit reinforced network increased, resulting in an increase in the density of high polarizability factor per unit volume, which led to an increase in the refractive index of the glass system.

[0034] The thermo-optical coefficient d of a single-sided polished sample in the range of 1.5–20 μm was measured using a variable-temperature infrared variable-angle ellipsometer. n / dT. First, fix the glass to be tested on the temperature control platform, and set the temperature range to 30~90℃. Test the refractive index of the sample every 10℃. After each temperature change, preheat for 20 minutes to reduce measurement error. Figures 9-11 The thermo-optic coefficient d of samples 1-3, 4-6, and 7-9. n A schematic diagram illustrating the change of / dT with temperature. (See diagram below.) Figures 9-11As shown, by linearly fitting the data of the refractive index n varying with temperature, the slope is the thermo-optic coefficient d n / dT value. The measurement results are shown in Table 2.

[0035] Generally speaking, the thermo-optic coefficient d n / dT is positively correlated with the magnitude of the refractive index n , and the higher the refractive n , the higher the thermo-optic coefficient d n / dT. The thermo-optic coefficient d n / dT of the sample in Comparative Example 1 is 61.8×10 −6 / K. For the acousto-optic chalcogenide glass samples of Examples 1 to 10 of the present invention, through the fine cooperative regulation of the glass network structure by Ga and Sn, while significantly increasing the refractive index n (such as in some examples n >2.6), the thermo-optic coefficient d n / dT does not increase by a multiple, but is stable at a relatively low level of (53.2~73.2)×10 −6 / K.

[0036] III. Mechanical property test: The Vickers hardness of a 2-mm double-sided polished sample was measured using a hardness indentation instrument H v , and the test results are shown in Table 1. For the samples of Examples 1 to 3, 4 to 6, and 7 to 9, as the Te content increases and the Se content decreases, the average coordination number remains unchanged, but the average bond energy decreases and the degree of structural crosslinking decreases, and the rigidity of the glass network weakens, and the change range of the Vickers hardness H v is 145.1~203.3 kg / mm 2 ; for the samples of Examples 4, 7, and 10, when the Sn content remains unchanged, as the Ga content increases, the internal structure of the glass becomes denser and the network rigidity increases, and the Vickers hardness H v increases from 171.4 kg / mm 2 to 203.3 kg / mm 2 . The density of the sample was measured using the Archimedes drainage method ρ , and the test results are shown in Table 1. The relative atomic masses of each element: Ga(69.72)<Se(78.96)<Sn(118.71)<Te(127.6). For the samples of Examples 1 to 3, 4 to 6, and 7 to 9, as the Te content increases and the Se content decreases, the density increases with the increase of the total atomic mass.

[0037] IV. Laser Damage Threshold Test: The laser damage threshold test was conducted according to the national standard (GB / T 16601.2-2017) using the S-on-1 damage probability method. Before the laser damage test, the glass sample was inspected using a perspective imaging system to confirm its optical homogeneity by removing streaks, bubbles, etc. The glass sample was irradiated for 1 second with lasers of different energy densities (1.55 µm wavelength, 5 kHz repetition frequency, 20 ns pulse width). At least 10 points were irradiated at each laser energy density to obtain the corresponding damage probability. The corresponding positions were recorded on a coordinate system of laser energy density and damage probability. A linear fit was then performed on these probabilities; the intersection of this line with the energy axis is the zero-probability damage threshold, i.e., the laser damage threshold of the glass sample. The laser damage thresholds of samples from Examples 1-10 and Comparative Examples 1, 2, and 5 are shown in Table 2. As can be seen from Table 2, the optical band gaps of samples from Examples 1-3, 4-6, and 7-9 are... E opg The laser damage threshold decreases with increasing Te content. F th The decrease is due to the increased number of weak bond energies, such as Te-related heteropolar bonds, within the glass, but its minimum value is still lower than that of Ge. 33 As 12 Se 55 (2.46 J / cm) 2 It needs to be high.

[0038] Table 2: Optical bandgap, laser damage threshold, acousto-optic properties, and thermo-optic coefficients of samples from Examples 1-10 and Comparative Examples 1, 2, and 5

[0039] V. Raw Material Cost Comparison: This invention, through its germanium-free composition design, utilizes relatively inexpensive gallium, tin, and high-purity tellurium to synergistically construct a glass network, significantly reducing raw material procurement costs. Quantitative scientific calculations show that, under the same 5N-grade high-purity raw material conditions, the raw material cost of 1kg of the Ga-Sn-Se-Te product of this invention is only approximately 820 yuan, significantly lower than that of traditional commercial acousto-optic chalcogenide glass (Ge-Sn-Se-Te) containing germanium. 33 As 12 Se 55 The cost (approximately RMB 5608.3 / kg) is reduced by about 85%, fundamentally solving the technical pain points of high production costs and significant price fluctuations in the international market caused by the high dependence on expensive raw material germanium in traditional acoustic and optical materials. This results in extremely high industrialization cost-effectiveness and market competitiveness. Furthermore, the chalcogenide glasses in Examples 1-10 do not contain toxic or heavy metal elements such as As and Sb, making them environmentally friendly.

[0040] In summary, the present invention Ga x Sny Se 100-x-y-z Te z Acousto-optic chalcogenide glasses possess advantages such as extremely high acousto-optic quality factors, low acoustic attenuation, high laser damage threshold, and high transmittance in the near-infrared band. The acousto-optic performance data of Examples 1-10 and Comparative Examples 1 and 2 were imported into MATLAB software to obtain... Figure 12 The five-dimensional relationship diagram of the acousto-optic properties shown demonstrates that the present invention utilizes Ga... x Sn y Se 100-x-y-z Te z Optimization of the composition of acousto-optic chalcogenide glasses yielded Ga with excellent acousto-optic properties. x Sn y Se 100-x-y-z Te z Acousto-optic chalcogenide glass composition, with As2S3, Ge 33 As 12 Se 55 Compared with commercially available acousto-optical chalcogenide glass, it has significant performance advantages.

Claims

1. An environmentally friendly chalcogenide glass material with excellent acoustic and optical properties, characterized in that, The chemical formula of this chalcogenide glass material is Ga. x Sn y Se 100-x-y-z Te z Where x, y, and z are the mole fractions of Ga, Sn, and Te, respectively, x = 5~10, y = 15~20, and z = 3~7. The microstructure of this chalcogenide glass material contains a stable [GaTe] group. n Se 4-n ] and [SnTe n Se 4-n The structure is tetrahedral, and the value of n can be 0, 1, 2, 3 or 4.

2. The environmentally friendly chalcogenide glass material with excellent acoustic and optical properties according to claim 1, characterized in that, The acousto-optic quality factor of the chalcogenide glass material at a wavelength of 1.55 µm M The range of 2 is (332.36~456.61)×10 -18 s 3 / g, refractive index n The value is 2.566~2.

628.

3. The environmentally friendly chalcogenide glass material with excellent acoustic and optical properties according to claim 1, characterized in that, The thermo-optic coefficient d of the chalcogenide glass material n / dT is (53.21~73.35)×10 -6 / K, the ultrasonic attenuation coefficient at a 10 MHz ultrasonic frequency α The variation range is 4.12~6.28 dB / cm.

4. The environmentally friendly chalcogenide glass material with excellent acoustic and optical properties according to claim 1, characterized in that, The chalcogenide glass material has a full transmittance band covering the infrared band of 0.8~25 µm, with a maximum transmittance of 60~65%.

5. The environmentally friendly chalcogenide glass material with excellent acoustic and optical properties according to claim 1, characterized in that, The optical band gap of the chalcogenide glass material E opg The laser damage threshold is 1.06~1.32 eV. F th The range is 3.16~5.35 J / cm. 2 .

6. The application of the environmentally friendly chalcogenide glass material with excellent acoustic and optical properties as an acoustic and optical medium in the field of acoustics and optics, as described in any one of claims 1 to 5.

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