Ultralow-cost Ga-Sn-Se acousto-optic chalcogenide glass and application thereof

Abstract

The invention discloses ultralow-cost Ga-Sn-Se acousto-optic chalcogenide glass, the chemical composition formula of the acousto-optic chalcogenide glass is GaxSnySe100-x-y, x is the mole fraction of Ga, y is the mole fraction of Sn, x is more than or equal to 5 and less than or equal to 15, y is more than or equal to 14 and less than or equal to 20, and a basic network unit of a glass frame of the acousto-optic chalcogenide glass comprises a stable tetrahedral structure taking Ga or Sn as a center and an ethane-like structure of Ga-Ga bonds. The acousto-optic chalcogenide glass has good acousto-optic characteristics, the acousto-optic quality factor M2 under the wavelength of 1550 nm is 213 * 10 <-18 > s3 / g to 261 * 10 <-18 > s3 / g, the ultrasonic attenuation alpha under the ultrasonic frequency of 10 MHz is 3.27 dB / cm to 5.09 dB / cm, the acousto-optic chalcogenide glass can be widely applied to the acousto-optic field as an acousto-optic medium, and the acousto-optic chalcogenide glass has the advantage of ultralow cost, does not contain toxic or heavy metal elements such as As, Sb and the like, is eco-friendly, and can be widely applied to the acousto-optic field. And human health is not harmed.

Description

Technical Field

[0001] This invention relates to the field of acousto-optic materials, specifically to an ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass and its applications. Background Technology

[0002] Acousto-optic devices (AODs) 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 laser technology, radar systems, and other fields. The core components of an ACD device mainly consist of a piezoelectric transducer and an acousto-optic medium material. The quality of the acousto-optic medium material determines the performance of the ACD device. With the development of laser technology and lasers, ACD devices are trending towards lower power consumption, higher laser power processing capabilities, mid-infrared operating bands, and miniaturization. Currently, the commonly used commercial acousto-optic crystal material TeO2 suffers from drawbacks such as a low acousto-optic quality factor M2 (i.e., acousto-optic figure of merit M2), a small infrared transmission range, and difficulties in large-size fabrication, making it difficult to meet the development requirements of high-performance infrared acousto-optic devices. Therefore, the development of novel acousto-optic medium materials is urgently needed.

[0003] Chalcogenide glasses possess advantages such as a high acousto-optic quality factor (M²), a wide infrared transmittance range, and ease of large-scale manufacturing. However, currently commercially available chalcogenide acousto-optic materials generally contain As, Sb, and Ge. As and Sb are toxic heavy metals, posing potential threats to the ecological environment and human health, while the high price of Ge raw materials hinders the commercialization of acousto-optic devices. Therefore, there is an urgent need to develop environmentally friendly chalcogenide acousto-optic materials that offer both good performance and low cost. Summary of the Invention

[0004] The technical problem to be solved by this invention is to provide an ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass and its application, which addresses the limitations of existing commercial chalcogenide acousto-optic materials due to their toxic elements and high cost. This Ga-Sn-Se acousto-optic chalcogenide glass has the advantages of low cost and environmental friendliness, and exhibits excellent comprehensive properties.

[0005] The technical solution adopted by this invention to solve the above-mentioned technical problems is: an ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass, wherein the chemical formula of the acousto-optic chalcogenide glass is Ga x Sn y Se 100-x-y Where x is the mole fraction of Ga, y is the mole fraction of Sn, 5≤x≤15, 14≤y≤20, the basic network unit of the glass frame of this acousto-optic chalcogenide glass includes a stable tetrahedral structure centered on Ga or Sn and an ethane-like structure with Ga-Ga bonds.

[0006] In a preferred embodiment, x = 5 and y = 14.

[0007] In another preferred embodiment, x = 15, y = 18.

[0008] Preferably, the acousto-optic chalcogenide glass has a full transmission band covering the infrared band, with a maximum transmittance of 60% to 70%.

[0009] Preferably, the acousto-optic chalcogenide glass has an acousto-optic quality factor M² of 213 × 10⁻⁶ at a wavelength of 1550 nm. -18 s 3 / g~261×10 -18 s 3 / g, with an ultrasonic attenuation α of 3.27dB / cm to 5.09dB / cm at a 10MHz ultrasonic frequency.

[0010] Preferably, the acousto-optic chalcogenide glass has an optical band gap of 1.44 eV to 1.60 eV and a laser damage threshold of 3.48 J / cm. 2 ~4.80 J / cm 2 .

[0011] The above-mentioned ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass is used as an acousto-optic medium in the acousto-optic field.

[0012] Compared with the prior art, the present invention has the following advantages:

[0013] 1. The chemical formula of the acousto-optic chalcogenide glass of this invention is Ga. x Sn y Se 100-x-y In this ternary system, the Sn element can neutralize oxygen-related impurities inside the glass, giving it excellent infrared transmittance. Furthermore, the basic network unit of the Ga-Sn-Se acousto-optic chalcogenide glass of this invention comprises a stable tetrahedral structure centered on Ga or Sn and an ethane-like structure with partial Ga-Ga bonds, exhibiting good acousto-optic properties. Its acousto-optic quality factor M² at 1550 nm wavelength is 213 × 10⁻⁶. -18 s 3 / g~261×10 -18 s 3 / g, with an ultrasonic attenuation α of 3.27dB / cm~5.09dB / cm at a 10MHz ultrasonic frequency, can be widely used as an acousto-optic medium in the acousto-optic field;

[0014] 2. The Ga-Sn-Se acousto-optic chalcogenide glass of this invention has the advantage of ultra-low cost. According to current market prices, based on high-purity raw materials with a purity of 5N, the price of 1 kg of the Ga-Sn-Se acousto-optic chalcogenide glass of this invention is 652.3 to 749.2 yuan, which is only a fraction of the price of commercially available chalcogenide acousto-optic material Ge 33 As 12 Se 5511.6% to 13.4% of the price;

[0015] 3. The Ga-Sn-Se acousto-optic chalcogenide glass of this invention is environmentally friendly, does not contain toxic or heavy metal elements such as As and Sb, is eco-friendly, and does not harm human health. Attached Figure Description

[0016] Figure 1 Infrared transmission spectra of the acousto-optic chalcogenide glasses of Examples 1-6;

[0017] Figure 2 The ultrasonic attenuation α and longitudinal wave velocity v of the chalcogenide glass samples in Examples 1, 3, and 6. L Schematic diagram showing the change with Ga content;

[0018] Figure 3 The diagram shows the structural changes of the basic network units in the chalcogenide glass samples of Examples 1, 3, and 6.

[0019] Figure 4 The ultrasonic attenuation α and longitudinal wave velocity v of the chalcogenide glass samples in Examples 2-4 L Schematic diagram showing the change with Sn content;

[0020] Figure 5 This is a schematic diagram showing the change of the acousto-optic quality factor M2 of the chalcogenide glass samples in Examples 1-6 as a function of MCN.

[0021] Figure 6 The graph shows the relationship between ultrasonic attenuation α and acousto-optic quality factor M2 for chalcogenide glass samples of Examples 1-6 and Comparative Examples 1 and 4. Detailed Implementation

[0022] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0023] Six examples and four comparative examples of the Ga-Sn-Se acousto-optic chalcogenide glass of the present invention were selected. The chemical formulas of the acousto-optic chalcogenide glasses in Examples 1 to 6 are Ga... 15 Sn 18 Se 67 Ga 10 Sn 16 Se 74 Ga 10 Sn 18 Se 72 Ga 10 Sn 20 Se 70 Ga5Sn 14 Se 81 Ga5Sn 18 Se 77The chemical compositions of the acousto-optic chalcogenide glasses in Comparative Examples 1–4 are Ge, Ge, and Ge, respectively. 35 As 15 S 50 、Ge 33 As 12 Se 55 、Ge 12 Sb 32 S 56 、Ge 28 Sb 12 Se 60 Based on the raw material market price as of June 3, 2025, the raw material cost per kilogram of the acousto-optic chalcogenide glasses of Examples 1-6 and Comparative Examples 1-4 was calculated using high-purity raw materials with a purity of 5N. The calculation results are shown in Table 1. As can be seen from Table 1, compared to the acousto-optic chalcogenide glasses of Comparative Examples 1-4, the acousto-optic chalcogenide glasses of Examples 1-6 have an ultra-low cost; their raw material cost is only a fraction of that of commercial chalcogenide acousto-optic materials in Comparative Example 2 (Ge). 33 As 12 Se 55 The content of arsenic-optic chalcogenide glass ranges from 11.6% to 13.4%. Furthermore, the acousto-optic chalcogenide glasses of Examples 1-6 do not contain toxic or heavy metal elements such as As and Sb, exhibiting environmentally friendly characteristics. Energy dispersive spectroscopy (EDS) tests were performed on the acousto-optic chalcogenide glasses of Examples 1-6, and the average coordination number (MCN) was calculated based on the actual composition. The results are shown in Table 1.

[0024] Table 1

[0025] Glass Number Glass composition Raw material cost (RMB / kg) Mean coordination number MCN Example 1 <![CDATA[Ga 15 Sleep 18 With 67 ]]> 749.2 2.613 Example 2 <![CDATA[Ga 10 Sleep 16 With 74 ]]> 700.9 2.489 Example 3 <![CDATA[Ga 10 Sleep 18 With 72 ]]> 700.5 2.536 Example 4 <![CDATA[Ga 10 Sleep 20 With 70 ]]> 700.1 2.577 Example 5 <![CDATA[Ga5Sn 14 With 81 ]]> 652.3 2.354 Example 6 <![CDATA[Ga5Sn 18 With 77 ]]> 652.4 2.46 Comparative Example 1 <![CDATA[Ge 35 As 15 S 50 ]]> 8263.3 - Comparative Example 2 <![CDATA[Ge 33 As 12 Se 55 ]]> 5608.3 - Comparative Example 3 <![CDATA[Ge 12 Sb 32 S 56 ]]> 2923.8 - Comparative Example 4 <![CDATA[Ge 28 Sat 12 With 60 ]]> 4628.2 -

[0026] The acousto-optic chalcogenide glasses of Examples 1-6 and Comparative Examples 1-4 were prepared using a vacuum melting and quenching method. The specific preparation methods included the following steps:

[0027] (1) According to the chemical composition formula of chalcogenide glass, accurately weigh the 5N purity elemental raw material of chalcogenide glass, mix the weighed raw materials evenly and place them in a quartz ampoule; evacuate the quartz tube to a vacuum degree of 10. -3 After Pa, the quartz tube is sealed with an oxyhydrogen flame;

[0028] (2) Place the sealed quartz tube into a swing furnace and swing it at 800-900°C for 10-12 hours; when the temperature inside the furnace drops to 600-700°C, take the quartz tube out of the swing furnace and quench it with compressed air until the surface of the glass melt separates from the inner wall of the quartz tube.

[0029] (3) Place the quartz tube in a temperature setting below the glass transition temperature (T). g Anneal the glass rod in an annealing furnace at 5-20°C for 8-10 hours to release internal stress. Remove the glass rod after annealing.

[0030] (4) Cut the chalcogenide glass rod into slices and polish them for later use.

[0031] The following tests were conducted on the acousto-optic chalcogenide glass samples from Examples 1-6 and Comparative Examples 1-4 to determine their different properties:

[0032] 1) Optical property testing: The infrared transmission spectra of the acousto-optic chalcogenide glasses of Examples 1-6 were measured using a visible-near-infrared spectrophotometer and a Fourier transform infrared spectrometer. The results are as follows: Figure 1 As shown. By Figure 1 As can be seen, the acousto-optic chalcogenide glasses of Examples 1-6 have a full transmission band covering the infrared band, with a maximum transmittance of 60%-70%. The optical band gap of the acousto-optic chalcogenide glasses of Examples 1-6 was calculated based on the absorption spectrum, and the calculated optical band gap is 1.44 eV-1.60 eV.

[0033] 2) Acousto-optic properties testing: Acousto-optic properties include the acousto-optic quality factor M2 and ultrasonic attenuation α.

[0034] The parameters required for calculating the acousto-optic quality factor M2 include refractive index n and photoelastic coefficient p. 12 Density ρ and longitudinal wave velocity v L The refractive index n of the chalcogenide glass sample at 1550 nm was measured using an infrared variable-angle ellipsometry; the photoelastic coefficient p of the chalcogenide glass sample at 1550 nm was measured using the Mach-Zehnder interferometry and with reference to standard BS 7604-1-1992. 12 The density ρ of the chalcogenide glass sample was measured using the Archimedes displacement method. The calculation results are shown in Table 1.

[0035] The longitudinal wave velocity v of chalcogenide glass samples was measured using the pulse-echo method and in accordance with the GB / T 5266-2006 standard. L With ultrasonic attenuation α, pulse signals are transmitted and received via a pulse transmitter and receiver and an ultrasonic probe with a center frequency of 10MHz. The longitudinal wave velocity v is calculated based on the time difference between adjacent main peaks and secondary peaks of the echo on the oscilloscope. L The ultrasonic attenuation α is measured based on the amplitude difference between adjacent primary and secondary peaks of the echo on the oscilloscope.

[0036] The acousto-optic quality factor M2 of the chalcogenide glass sample is calculated using the following formula:

[0037]

[0038] The calculated acousto-optic quality factor M2 of the chalcogenide glass samples in Examples 1-6 is shown in Table 2. As can be seen from Table 2, the overall variation range of the acousto-optic quality factor M2 for the chalcogenide glass samples in Examples 1-6 is 213 × 10⁻⁶. -18 s3 / g~261×10 -18 s 3 / g. As can be seen from the formula for calculating the acousto-optic quality factor M2, M2 depends on the refractive index n and the longitudinal wave velocity v. L The larger the refractive index n, the higher the longitudinal wave velocity v. L The smaller the value, the larger M2. As the Ga content increases, the [GaSe4] tetrahedral structure inside the glass gradually transforms into an [Se3Ga-GaSe3] ethane-like structure. Due to the high polarizability of the Ga-Ga homopolar bonds, the refractive index n increases significantly, and the acousto-optic quality factor M2 increases markedly. However, when the Sn content increases, the substitution of [Se8] rings by the [SnSe4] tetrahedral structure mainly occurs, i.e., the replacement of Se-Se bonds by Sn-Se bonds. The greater polarizability of the Sn-Se bonds leads to an increase in the refractive index n, but due to the simultaneous increase in the longitudinal wave velocity v... L As the α increases, the acoustic-optical quality factor M2 remains essentially unchanged.

[0039] Table 2

[0040]

[0041] Figure 2 The ultrasonic attenuation α and longitudinal wave velocity v of the chalcogenide glass samples in Examples 1, 3, and 6. L A schematic diagram showing the variation with Ga content. When ultrasound propagates inside the glass, it causes vibrations in the internal atoms and structural units, resulting in ultrasonic loss. The magnitude of this loss is influenced by the type of structural unit and the connectivity of the glass network. When the Sn content remains constant, as Ga, with its higher coordination number, gradually replaces Se, the average coordination number of the glass continuously increases, making the glass network structure denser and more stable. The structural changes of the basic network units in the chalcogenide glass samples of Examples 1, 3, and 6 are shown in the diagram. Figure 3 Therefore, the ultrasonic attenuation α decreases with increasing Ga content, ranging from 4.16 to 3.27 dB / cm, and the longitudinal wave velocity v L The value increases with increasing Ga content, and its range is 2.305 × 10⁻⁶. 5 ~2.528×10 5 cm / s. Figure 4 The ultrasonic attenuation α and longitudinal wave velocity v of the chalcogenide glass samples in Examples 2-4 L A schematic diagram illustrating the variation with Sn content. The mechanism is similar to that of Ga content changes; the ultrasonic attenuation decreases from 4.71 dB / cm to 3.74 dB / cm, and the longitudinal wave velocity v... L From 2.272×10 5 cm / s increased to 2.357 × 10 5cm / s. The overall range of ultrasonic attenuation α for the chalcogenide glass samples in Examples 1–6 was 3.27–5.09 dB / cm, and the longitudinal wave velocity v L The overall range of variation is 2.163 × 10⁻⁶. 5 ~2.528×10 5 cm / s.

[0042] Figure 5 This is a schematic diagram showing the variation of the acousto-optic quality factor M2 with MCN for the chalcogenide glass samples in Examples 1-6. Figure 5 As shown, the acoustic-optical quality factor M2 decreases as the MCN increases. Figure 6 The graph shows the relationship between ultrasonic attenuation α and the acousto-optic quality factor M2 for chalcogenide glass samples in Examples 1-6 and Comparative Examples 1 and 4. The chalcogenide glass samples in Examples 1-6 exhibit relatively balanced acousto-optic properties while being low-cost and environmentally friendly.

[0043] 3) Laser damage threshold related tests:

[0044] 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, ensuring the absence of streaks, bubbles, etc. The glass sample was irradiated for 1 second with lasers of different energy densities (1550 nm wavelength, 5 kHz repetition rate, 20 ns pulse width), with at least 10 points irradiated at each energy density. The corresponding damage probabilities were obtained, and the 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 and the energy axis represents the zero-probability damage threshold, i.e., the laser damage threshold of the glass sample. The glass transition temperature To of the glass sample was obtained using differential scanning calorimetry. g The Vickers hardness of glass samples was characterized using an indentation microhardness tester.

[0045] The laser damage threshold, optical band gap, glass transition temperature, and Vickers hardness of the chalcogenide glass samples from Examples 1-6 and Comparative Examples 1-2 are shown in Table 3. Generally, a large optical band gap and a high glass transition temperature T0 are preferred. g Materials with high Vickers hardness also exhibit higher laser damage thresholds. Overall, the chalcogenide glass samples in Examples 1–6 have relatively high laser damage thresholds, with Example 1 showing the highest at 4.80 J / cm². 2 This indicates that it has good resistance to light radiation and strong thermal stability.

[0046] Table 3

[0047]

[0048] In summary, the Ga-Sn-Se acousto-optic chalcogenide glass of this invention has the advantages of low cost and environmental friendliness, exhibits excellent comprehensive properties, and can be widely used as an acousto-optic medium in the acousto-optic field.

Claims

1. A low-cost Ga-Sn-Se acousto-optic chalcogenide glass, characterized in that, The chemical formula of this acousto-optic chalcogenide glass is Ga. x Sn y Se 100-x-y Where x is the mole fraction of Ga, y is the mole fraction of Sn, 5≤x≤15, 14≤y≤20, the basic network unit of the glass frame of this acousto-optic chalcogenide glass includes a stable tetrahedral structure centered on Ga or Sn and an ethane-like structure with Ga-Ga bonds.

2. The ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass according to claim 1, characterized in that, x = 5, y = 14.

3. The ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass according to claim 1, characterized in that, x = 15, y = 18.

4. The ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass according to claim 1, characterized in that, The acousto-optic chalcogenide glass has a full transmission band covering the infrared band, with a maximum transmittance of 60% to 70%.

5. The ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass according to claim 1, characterized in that, The acousto-optic quality factor M² of the acousto-optic chalcogenide glass at a wavelength of 1550 nm is 213 × 10⁻⁶. -18 s 3 / g~261×10 -18 s 3 / g, with an ultrasonic attenuation α of 3.27dB / cm to 5.09dB / cm at a 10MHz ultrasonic frequency.

6. The ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass according to claim 1, characterized in that, The acousto-optic chalcogenide glass has an optical band gap of 1.44 eV to 1.60 eV and a laser damage threshold of 3.48 J / cm². 2 ~4.80 J / cm 2 .

7. The application of the ultra-low cost Ga-Sn-Se acousto-optic chalcogenide glass as described in any one of claims 1 to 6 as an acousto-optic medium in the acousto-optic field.

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