Iii-a-v-a-va ternary compound semiconductor crystal and method of preparing and using same

Abstract

The application discloses a group IIIA-VIA-VIA ternary compound semiconductor crystal and a preparation method and application thereof, and belongs to the technical field of semiconductor materials. x B 1‑x C3 or A x B 1‑x C, wherein A and B are selected from two of In, Sb, Bi, Ge and Sn, C is selected from S, Se and Te, and 0 The application provides a preparation method combining a solid phase reaction and a chemical gas phase transport, which comprises nanometerization pretreatment of raw materials, packaging according to an optimized molar ratio in an inert atmosphere, low-temperature solid phase reaction of a swing furnace, double-temperature-zone chemical gas phase transport growth, and post-processing and device integration. The method realizes controllable preparation of various group IIIA-VIA-VIA ternary compound high-quality single crystals, and solves the problem that high-quality single crystals are difficult to obtain by using a traditional method. The obtained crystal has obvious in-plane optical anisotropy, and an optoelectronic device prepared based on the crystal exhibits excellent polarized light detection performance in a wide spectral range at room temperature, and is suitable for the fields of encrypted communication, optoelectronic sensing and integrated optoelectronic devices.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor materials, specifically relating to IIIA-VA-VIA group ternary compound semiconductor crystals, their preparation methods, and applications. Background Technology

[0002] Polarization detection has significant application value in fields such as complex environment detection, encrypted communication, and autonomous driving. Traditional polarization detection mainly relies on complex polarization optical elements or subwavelength metal wire grids, which face new challenges under the trend of information device integration and miniaturization. In recent years, low-dimensional semiconductor materials with in-plane anisotropic structures have shown the potential to achieve polarization detection and polarization imaging without using polarization optical elements or subwavelength metal wire grids.

[0003] However, most of the low-dimensional layered semiconductor materials developed so far are single-element or binary compound materials, such as black phosphorus (bP), purple phosphorus (vP), germanium selenide (GeSe), and bismuth sulfide (Bi2S3). These materials face the following technical bottlenecks when applied to high-performance polarization detection applications: 1. Difficulty in controlling material composition inhomogeneity, affecting intrinsic properties: Existing preparation methods are not refined enough in raw material processing, making it difficult to achieve nanoscale uniform mixing, resulting in uneven component distribution in the final product, directly affecting the photoelectric anisotropy and stability of the material; 2. Inaccurate stoichiometry, limiting material performance regulation: Existing technologies struggle to precisely control the proportions of multiple elements in ternary compounds, and insufficient purity of the reaction environment leads to the introduction of impurities, affecting the material's carrier concentration and optical properties; 3. Low crystal growth quality, making it difficult to obtain high-quality single crystals: Traditional solvothermal methods easily introduce organic impurities, resulting in solid-state... Sintering methods are difficult to obtain large-size single crystals, resulting in high crystal defect density and limiting the full realization of the intrinsic properties of the material; 4. The post-processing of materials and device integration processes are imperfect: Existing methods do not adequately purify the crystals after growth, and residues affect the material properties; at the same time, the crystal transfer and device integration processes have poor compatibility, resulting in low device fabrication yield and unstable performance; 5. The fabrication process has poor universality and is difficult to apply on a large scale: Most existing methods are for specific material systems, with narrow process parameter windows and a lack of system optimization, making it difficult to adapt to the preparation needs of different ternary compound systems, and large-scale preparation is costly and energy-intensive.

[0004] To address the aforementioned challenges, ternary compound semiconductor materials offer greater possibilities for designing novel high-performance polarization detectors due to their ability to flexibly control band structure and crystal structure by altering elemental ratios. However, developing a universally applicable, efficient, and high-quality method for preparing such ternary compound semiconductor single crystals, and achieving good integration with device fabrication processes, has become a critical technical problem that urgently needs to be solved in this field. This invention addresses these issues by proposing an innovative material system and preparation scheme. Summary of the Invention

[0005] This invention provides a group IIIA-VA-VIA ternary compound semiconductor crystal, its preparation method, and its applications. It aims to solve the problem of obtaining high-quality single crystals when preparing such materials using existing solvothermal and solid-state sintering methods. By employing a synergistic process combining solid-state reaction and chemical vapor transport (CVT), the common challenge of growing high-quality single crystals from ternary compounds is addressed. Furthermore, it provides a crystal growth method applicable to various compositions, with simple processing and controllable cost. The resulting crystals can be used in high-performance polarized light detection and encrypted communication, among other fields.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A group IIIA-VA-VIA ternary compound semiconductor crystal with the general chemical formula A x B 1-x C3 or A x B 1-x C, where A and B are selected from two metals in Group IIIA or Group VA, including In, Sb, Bi, Ge, and Sn; C is selected from nonmetals in Group VIA, including S, Se, and Te; The range of x is 0 < x < 1.

[0007] The semiconductor crystal includes, but is not limited to, the following compounds: In x Sb 1-x S3, In x Sb 1-x Se3、In x Sb 1-x Te3, Sb x Bi 1-x S3, Sb x Bi 1-x Se3、In x Bi 1-x S3, In x Bi 1-x Se3、In x Bi 1-x Te3, Bi x Sn 1-x S, Ge x Sn 1-x S3, Gex Sn 1- x Se3, Ge x Sn 1-x Te3.

[0008] Among them, In x Sb 1-x S3, In x Sb 1-x Se3, Sb x Bi 1-x S3, In x Bi 1-x S3, Bi x Sn 1-x S, Ge x Sn 1-x S3 exhibits significant in-plane optical anisotropy, making it suitable for polarized light detection and optical communication devices.

[0009] The present invention also provides a method for preparing the above-mentioned ternary compound semiconductor crystal, comprising the following steps: S1: Raw material pretreatment Bulk metals (In, Sb, Bi, Ge, Sn) and bulk non-metals (S, Se, Te) are crushed, pulverized, ball-milled, and sieved to obtain powders with particle sizes ranging from 50 nm to 200 nm.

[0010] S2: Ingredient Preparation and Packaging In an inert atmosphere glove box, weigh the corresponding metal and non-metal powders according to the metal to non-metal molar ratio of (0-1):(0-1):(3.05-3.55), add iodine particles as a chemical vapor transport agent, mix, and then pack into a quartz tube. In a high vacuum (not less than 2.5 × 10⁻⁶),... -2 Pa) lower sealing pipe opening.

[0011] S3: Solid-state reaction A sealed quartz tube is placed in a gyratory furnace and reacted at 220℃-450℃ for 2h-36h, while gyratory motion is performed (angle ±15°, rotation speed 24r / min to 70r / min) to achieve low-temperature solid-phase synthesis of the raw materials.

[0012] S4: Chemical Vapor Transport Growth After solidification, the quartz tube is transferred to a dual-temperature zone tube furnace. The high-temperature zone is set to 520°C to 1020°C, and the low-temperature zone is set to 450°C to 720°C. After heating and holding (holding time not exceeding 7200 min), it is naturally cooled. The crystal grows in the low-temperature zone through the action of iodine transport agent.

[0013] S5: Post-processing The grown crystals were ultrasonically cleaned in anhydrous ethanol for 10-30 minutes, and then subjected to vacuum (≤3×10⁻⁶). -3 Annealing at 150℃-220℃ for 60-120 minutes under Pa conditions removes residual iodine.

[0014] S6: Device Fabrication The crystal is transferred onto a substrate (such as Si, SiO2, c-Al2O3, or SiC), and then photolithography, metal electrode deposition (Au / Cr), lift-off, and wire bonding processes are performed to fabricate an optoelectronic device based on the ternary compound semiconductor.

[0015] This invention also relates to the application of the above-mentioned ternary compound semiconductor crystal in polarization detection, encrypted communication, photoelectric sensors and integrated optoelectronic devices.

[0016] Compared with the prior art, this patent application has the following advantages: 1. Refined raw material processing ensures uniform composition and high reactivity. Through a four-stage integrated process of crushing, pulverizing, ball milling, and sieving, bulk raw materials are precisely controlled to produce uniform nano-sized powders of 50-200 nm. This scientifically designed particle size range avoids the agglomeration effect of excessively fine powders while significantly increasing the specific surface area of ​​the raw materials, thereby improving their activity by more than 30%. The nano-sized particles exhibit excellent diffusion characteristics in subsequent solid-phase reactions, with atomic migration efficiency increased by approximately 2-3 times, ensuring sufficient contact and uniform mixing between different elements from the source. Example data shows that after using this pretreatment process, the elemental distribution uniformity of the product reaches over 98%, far exceeding the 75%-85% level of traditional coarse-particle raw materials.

[0017] 2. Precise control of formulation and environment ensures adjustable stoichiometry and reaction purity. Precise weighing was performed in an argon-protected glove box environment according to an optimized molar ratio of (0-1):(0-1):(3.05-3.55), achieving a measurement accuracy of ±0.1 mg. This ratio range has been validated through extensive experiments and can balance the requirements of stoichiometry and crystal growth kinetics. High-vacuum sealing technology was employed, with the vacuum level strictly controlled at 2.5 × 10⁻⁶. -2 The pH is above 1000 Pa, the oxygen content is below 1 ppm, and the moisture content is below 0.5 ppm. This ultra-high purity environment effectively prevents the raw materials from oxidizing and deteriorating at high temperatures, and avoids the formation of impurity phases. Experiments show that the intrinsic carrier concentration of crystals prepared using this process is reduced by an order of magnitude compared to materials prepared in a conventional atmospheric environment.

[0018] 3. Stepwise reaction synergy achieves precursor homogenization and high-quality single crystal growth. An innovative stepwise growth strategy of "solid-phase followed by gas-phase" is adopted. First, a solid-phase reaction is carried out at a relatively low temperature of 220-450℃, combined with ±15° rocking and a rotation speed of 24-70 r / min, to ensure thorough mixing of the reactants and the formation of a homogeneous ternary precursor. Subsequently, under precise temperature field control in the 520-1020℃ high-temperature region and the 450-720℃ low-temperature region, selective crystal growth is achieved through an iodine transport agent. Long-term heat preservation design allows the crystal growth rate to be controlled within an optimized range of 1-5 μm / h. This stepwise synergistic mechanism reduces the crystal defect density from 10 times that of traditional methods. 8 / cm 2 Reduced to 10 5 / cm 2 The crystal size is then increased from the micrometer level to the millimeter level.

[0019] 4. Post-processing is compatible with device integration processes, ensuring material purity and device fabrication feasibility. A multi-step purification process was adopted: first, the surface physical adsorbates were removed by ultrasonic cleaning with anhydrous ethanol, and then the purification process was carried out in a process with a concentration of ≤3×10⁻⁶. - 3 Annealing at ultra-high vacuum (Pa) and 150-220℃ reduces iodine residue from the initial 0.5-1% to below 0.01%. In device integration, flexible media such as PDMS and PC are used for non-destructive crystal transfer, achieving a success rate of over 95%. Electrode fabrication processes compatible with standard CMOS techniques (1μm lithography accuracy, <10Ω electrode contact resistance) increase device yield from 60% using traditional methods to over 90%.

[0020] 5. The process parameters are systematically optimized, with strong universality and scalability potential. Key process parameters have been validated through systematic optimization experiments: raw material particle size 50-200 nm, solid-phase reaction temperature 220-450℃, gas-phase transport temperature gradient 70-300℃, holding time ≥120 h, and annealing temperature 150-220℃. This parameter system is applicable to multiple ternary systems such as In-Sb-S(Se,Te), Sb-Bi-S(Se), In-Bi-S(Se,Te), Bi-Sn-S, and Ge-Sn-S(Se,Te), with a material compatibility rate exceeding 90%. All process equipment is conventional material growth equipment, capable of processing 10-20 quartz tubes per batch, demonstrating good potential for process scale-up. Cost analysis shows that compared to traditional single-crystal preparation methods, this process can reduce energy consumption by approximately 40% and increase raw material utilization by 25%.

[0021] In summary, this invention not only provides a series of novel ternary compound semiconductor crystals with significant in-plane optical anisotropy (anisotropy ratios of 2.5-4.0), but also establishes a controllable, efficient, and low-cost high-quality single-crystal fabrication platform. The polarization detector fabricated based on this material achieves a responsivity of 10. 3 With an A / W ratio on the order of magnitude and a polarization extinction ratio exceeding 10, it exhibits excellent detection performance in a wide spectral range (275-1600nm) at room temperature, providing a solid technical foundation for the development of next-generation optoelectronic devices. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the process flow of Embodiment 1 of this application.

[0023] Figure 2 The image shows a crystal of GeSnS3 obtained in Example 1 of this application.

[0024] Figure 3 The image obtained in Example 1 of this application is a scanning electron microscope image of GeSnS3 semiconductor material.

[0025] Figure 4 This represents the distribution ratio of GeSnS3 elements in Embodiment 1 of this application.

[0026] Figure 5 The It curves of the device based on GeSnS3 material in Example 1 of this application are shown in the range of 275~630nm.

[0027] Figure 6 This is a crystal image of InSbSe3 obtained in Example 2 of this application.

[0028] Figure 7 The image obtained in Example 2 of this application is a scanning electron microscope image of the InSbSe3 semiconductor material.

[0029] Figure 8 This represents the distribution ratio of InSbSe3 elements in Embodiment 2 of this application.

[0030] Figure 9 In Embodiment 2 of this application, an InSbSe3 device is used as a receiver to transmit an ASCII-encoded "HTU" signal.

[0031] Figure 10 This is a crystal image of SbBiS3 obtained in Example 3 of this application.

[0032] Figure 11 This is the polarization response of the SbBiS3 device used in Embodiment 3 of this application.

[0033] Figure 12 This is a crystal image of InSbS3 obtained in Example 4 of this application.

[0034] Figure 13 Bi obtained in Example 5 of this application 0.02 Image of SnS crystal.

[0035] Figure 14 The Ge obtained in Example 6 of this application 0.04 Sn 0.96 Crystal image of S2. Detailed Implementation

[0036] To make the technical solution and advantages of the present invention clearer, the implementation of the present invention will be described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the scope of protection of the present invention.

[0037] Example 1 The method for preparing GeSnS3 crystals and integrating them into devices includes the following steps: Step S1: Raw material pretreatment Using a crusher, pulverizer, ball mill, and vibrating screen, bulk metals Ge and Sn are progressively crushed and sieved to a particle size of approximately 120 nm.

[0038] Step S2: Ingredient preparation and packaging Weigh out 0.504 g of Ge powder, 0.824 g of Sn powder, and 0.668 g of S powder (metal to nonmetal molar ratio of 1:1:3.06) in an inert atmosphere glove box, and add 80 mg of iodine granules as a transport agent. Transfer the mixture to the bottom of a quartz tube and seal it using a high-vacuum tube sealing machine at a vacuum degree of 2.2 × 10⁻⁶. -2 The quartz tube is sealed under the conditions of Pa and a rotation speed of 1.5 r / s.

[0039] Step S3: Solid-state reaction The sealing tube was placed in a swing furnace, and the reaction temperature was set to 450℃, the reaction time to 12 h, the swing angle to ±15°, and the rotation speed to 32 r / min for low-temperature solid-phase reaction.

[0040] Step S4: Chemical vapor transport growth The reacted quartz tube was transferred to a dual-temperature zone tube furnace, with a high-temperature zone of 726°C and a low-temperature zone of 520°C. The heating time was 120 min, and the holding time was 5760 min. Then, it was naturally cooled to room temperature to achieve the vapor-phase transport growth of GeSnS3 crystals.

[0041] Step S5: Post-processing The growth product was ultrasonically cleaned in anhydrous ethanol for 30 min, followed by cleaning under a vacuum of less than 3 × 10⁻⁶. -3Annealing at 180°C for 60 min under Pa conditions to remove residual iodine transporter.

[0042] Step S6: Device fabrication GeSnS3 crystals were transferred onto a SiO2 / Si substrate using polydimethylsiloxane (PDMS) combined with a two-dimensional transfer platform. Following photolithography, Au / Cr electrode deposition, lift-off, and wire bonding processes, GeSnS3-based semiconductor devices were fabricated.

[0043] Example 2 The method for preparing InSbSe3 crystals and integrating them into devices includes the following steps: Step S1: Raw material pretreatment Using a crusher, pulverizer, ball mill, and vibrating screen, bulk metals In and Sb are progressively crushed and sieved to a particle size of approximately 150 nm.

[0044] Step S2: Ingredient preparation and packaging Weigh out 0.482 g of In powder, 0.516 g of Sb powder, and 1 g of Se powder (metal to nonmetal molar ratio of 1:1:3.13) in an inert atmosphere glove box, and add 40 mg of iodine granules as a transport agent. Transfer the mixture to the bottom of a quartz tube and seal it using a high-vacuum tube sealing machine at a vacuum degree of 2.4 × 10⁻⁶. -2 The quartz tube is sealed under the conditions of Pa and quartz tube rotation speed of 1 r / s.

[0045] Step S3: Solid-state reaction The sealing tube was placed in a swing furnace, and the reaction temperature was set to 450℃, the reaction time to 16 h, the swing angle to ±15°, and the rotation speed to 37 r / min for low-temperature solid-phase reaction.

[0046] Step S4: Chemical vapor transport growth The reacted quartz tube was transferred to a dual-temperature zone tube furnace, with a high-temperature zone of 726°C and a low-temperature zone of 520°C. The heating time was 120 min, and the holding time was 5760 min. Then, it was naturally cooled to room temperature to achieve vapor-phase transport growth of InSbSe3 crystals.

[0047] Step S5: Post-processing The growth product was ultrasonically cleaned in anhydrous ethanol for 30 min, followed by cleaning under a vacuum of less than 3 × 10⁻⁶. -3 Annealing at 180°C for 60 min under Pa conditions to remove residual iodine transporter.

[0048] Step S6: Device fabrication InSbSe3 crystals were transferred onto a SiO2 / Si substrate using a polycarbonate (PC) and a two-dimensional transfer platform. Following photolithography, Au / Cr electrode deposition, lift-off, and wire bonding processes, InSbSe3-based semiconductor devices were fabricated.

[0049] Example 3 The method for preparing and integrating SbBiS3 crystals into devices includes the following steps: Step S1: Raw material pretreatment Using a crusher, pulverizer, ball mill, and vibrating screen, bulk metals Sb and Bi are progressively crushed and sieved to a particle size of approximately 80 nm.

[0050] Step S2: Ingredient preparation and packaging Weigh out 0.57 g of Sb powder, 0.97 g of Bi powder, and 0.47 g of S powder (metal to nonmetal molar ratio of 1:1:3.2) in an inert atmosphere glove box, and add 20 mg of iodine granules as a transport agent. Transfer the mixture to the bottom of a quartz tube and seal it using a high-vacuum tube sealing machine at a vacuum of 2.2 × 10⁻⁶. -2 The quartz tube is sealed under the conditions of Pa and a rotation speed of 1.5 r / s.

[0051] Step S3: Solid-state reaction The sealing tube was placed in a swing furnace, and the reaction temperature was set to 510℃, the reaction time to 18 h, the swing angle to ±15°, and the rotation speed to 32 r / min for a low-temperature solid-phase reaction.

[0052] Step S4: Chemical vapor transport growth The reacted quartz tube was transferred to a dual-temperature zone tube furnace, with a high-temperature zone of 550°C and a low-temperature zone of 450°C. The heating time was 120 min, and the holding time was 5760 min. The tube was then naturally cooled to room temperature to achieve vapor-phase transport growth of SbBiS3 crystals.

[0053] Step S5: Post-processing The growth product was ultrasonically cleaned in anhydrous ethanol for 30 min, followed by cleaning under a vacuum of 2.6 × 10⁻⁶. -3 Annealing at 170°C for 60 min under Pa conditions to remove residual iodine transporter.

[0054] Step S6: Device fabrication SbBiS3 crystals were transferred onto a SiO2 / Si substrate using polydimethylsiloxane (PDMS) combined with a two-dimensional transfer platform. Following photolithography, Au / Cr electrode deposition, lift-off, and wire bonding processes, SbBiS3-based semiconductor devices were fabricated.

[0055] Example 4 The method for preparing InBiS3 crystals and integrating them into devices includes the following steps: Step S1: Raw material pretreatment Using a crusher, pulverizer, ball mill, and vibrating screen, bulk metals In and Bi are progressively crushed and sieved to a particle size of approximately 150 nm.

[0056] Step S2: Ingredient preparation and packaging Weigh out 0.486 g of In powder, 0.518 g of Bi powder, and an appropriate amount of S powder (metal to nonmetal molar ratio of 1:1:3.06) in an inert atmosphere glove box, and add 80 mg of iodine granules as a transport agent. Transfer the mixture to the bottom of a quartz tube and seal it using a high-vacuum tube sealing machine at a vacuum degree of 2.4 × 10⁻⁶. -2 The quartz tube is sealed under the conditions of Pa and quartz tube rotation speed of 1 r / s.

[0057] Step S3: Solid-state reaction The sealing tube was placed in a swing furnace, and the reaction temperature was set to 450℃, the reaction time to 16 h, the swing angle to ±15°, and the rotation speed to 37 r / min for low-temperature solid-phase reaction.

[0058] Step S4: Chemical vapor transport growth The reacted quartz tube was transferred to a dual-temperature zone tube furnace, with a high-temperature zone of 720°C and a low-temperature zone of 520°C. The heating time was 60 min, and the holding time was 2880 min. Then, it was naturally cooled to room temperature to achieve vapor-phase transport growth of InBiS3 crystals.

[0059] Step S5: Post-processing The growth product was ultrasonically cleaned in anhydrous ethanol for 30 min, followed by cleaning under a vacuum of less than 3 × 10⁻⁶. -3 Annealing at 180°C for 60 min under Pa conditions to remove residual iodine transporter.

[0060] Step S6: Device fabrication InBiS3 crystals were transferred onto a SiO2 / Si substrate using polydimethylsiloxane (PDMS) combined with a two-dimensional transfer platform. Following photolithography, Au / Cr electrode deposition, lift-off, and wire bonding processes, InBiS3-based semiconductor devices were fabricated.

[0061] Example 5 Bi 0.02 Sn 0.98 The method for preparing SnS crystals and integrating them into devices includes the following steps: Step S1: Raw material pretreatment Using a crusher, pulverizer, ball mill, and vibrating screen, bulk metals Bi and Sn are progressively crushed and sieved to a particle size of approximately 100 nm.

[0062] Step S2: Ingredient preparation and packaging Weigh out 0.17 g of Bi powder, 0.1 g of Sn powder, and 0.026 g of S powder (metal to nonmetal molar ratio of 1:1:1) in an inert atmosphere glove box, and add 50 mg of iodine granules as a transport agent. Transfer the mixture to the bottom of a quartz tube and seal it using a high-vacuum tube sealing machine at a vacuum degree of 2.2 × 10⁻⁶. -2 The quartz tube is sealed under the conditions of Pa and a rotation speed of 1.5 r / s.

[0063] Step S3: Solid-state reaction The sealing tube was placed in a swing furnace, and the reaction temperature was set to 450℃, the reaction time to 12 h, the swing angle to ±15°, and the rotation speed to 32 r / min for low-temperature solid-phase reaction.

[0064] Step S4: Chemical vapor transport growth The reacted quartz tube was transferred to a dual-temperature zone tube furnace, with a high-temperature zone of 756°C and a low-temperature zone of 560°C. The heating time was 120 min, and the holding time was 5760 min. It was then allowed to cool naturally to room temperature to achieve Bi 0.02 Sn 0.98 Vapor phase transport growth of SnS crystals.

[0065] Step S5: Post-processing The growth product was ultrasonically cleaned in anhydrous ethanol for 30 min, followed by cleaning under a vacuum of less than 3 × 10⁻⁶. -3 Annealing at 180°C for 60 min under Pa conditions to remove residual iodine transporter.

[0066] Step S6: Device fabrication Using polydimethylsiloxane (PDMS) combined with a two-dimensional transfer platform, Bi 0.02 SnS crystals were transferred onto a SiO2 / Si substrate. Following photolithography, Au / Cr electrode deposition, lift-off, and wire bonding processes, a Bi-based... 0.02 Sn 0.98 Fabrication of SnS semiconductor devices.

[0067] Example 6 Ge 0.04 Sn 0.96 The method for fabricating and integrating S2 crystals into devices includes the following steps: Step S1: Raw material pretreatment Using a crusher, pulverizer, ball mill, and vibrating screen, bulk metals Ge and Sn are progressively crushed and sieved to a particle size of approximately 160 nm.

[0068] Step S2: Ingredient preparation and packaging Weigh out 0.456 g of Ge powder, 0.736 g of Sn powder, and 0.8 g of S powder (metal to nonmetal molar ratio of 1:1:4) in an inert atmosphere glove box, and add 80 mg of iodine granules as a transport agent. Transfer the mixture to the bottom of a quartz tube and seal it using a high-vacuum tube sealing machine at a vacuum degree of 2.2 × 10⁻⁶. -2 The quartz tube is sealed under the conditions of Pa and a rotation speed of 1.5 r / s.

[0069] Step S3: Solid-state reaction The sealing tube was placed in a swing furnace, and the reaction temperature was set to 450℃, the reaction time to 12 h, the swing angle to ±15°, and the rotation speed to 32 r / min for low-temperature solid-phase reaction.

[0070] Step S4: Chemical vapor transport growth The reacted quartz tube was transferred to a dual-temperature zone tube furnace, with the high-temperature zone set at 726°C and the low-temperature zone at 525°C. The heating time was 120 min, and the holding time was 5760 min. It was then allowed to cool naturally to room temperature to achieve Ge 0.04 Sn 0.96 Vapor transport growth of S2 crystals.

[0071] Step S5: Post-processing The growth product was ultrasonically cleaned in anhydrous ethanol for 30 min, followed by cleaning under a vacuum of less than 3 × 10⁻⁶. -3 Annealing at 180°C for 60 min under Pa conditions to remove residual iodine transporter.

[0072] Step S6: Device fabrication Using polydimethylsiloxane (PDMS) combined with a two-dimensional transfer platform, Ge 0.04 Sn 0.96 S2 crystals were transferred onto a SiO2 / Si substrate. Following photolithography, Au / Cr electrode deposition, lift-off, and wire bonding processes, a Ge-based substrate was successfully fabricated. 0.04 Sn 0.96 Semiconductor device fabrication for S2.

[0073] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A IIIA-VA-VIA group ternary compound semiconductor crystal, characterized in that, Its general chemical formula is A x B 1-x C3 or A x B 1-x C, where A and B are selected from two metals in Group IIIA or Group VA, namely In, Sb, Bi, Ge, and Sn; C is selected from nonmetals in Group VIA, namely S, Se, and Te; and the value of x is in the range of 0 < x < 1.

2. The IIIA-VA-VIA group ternary compound semiconductor crystal according to claim 1, characterized in that, The semiconductor crystal is selected from: In x Sb 1-x S3, In x Sb 1-x Se3、In x Sb 1-x Te3, Sb x Bi 1-x S3, Sb x Bi 1-x Se3、In x Bi 1-x S3, In x Bi 1-x Se3、In x Bi 1-x Te3, Bi x Sn 1-x S, Ge x Sn 1-x S3, Ge x Sn 1-x Se3, Ge x Sn 1-x At least one of Te3.

3. The IIIA-VA-VIA group ternary compound semiconductor crystal according to claim 1 or 2, characterized in that, The crystal has in-plane optical anisotropy.

4. A method for preparing a IIIA-VA-VIA group ternary compound semiconductor crystal as described in any one of claims 1-3, characterized in that, Includes the following steps: S1. Raw material pretreatment: The bulk metal and bulk non-metal are crushed, pulverized, ball-milled and sieved to obtain powder with a particle size of 50-200 nm. S2. Ingredients and Packaging: In an inert atmosphere glove box, weigh the corresponding metal powder and non-metal powder according to the metal to non-metal molar ratio (0-1):(0-1):(3.05-3.55), add iodine particles as a transport agent, mix and pack into a quartz tube, and seal the tube opening under high vacuum conditions. S3, Solid-phase reaction: Place the sealed quartz tube in a gyratory furnace and react at 220-450℃ for 2-36 h while gyrating. S4. Chemical vapor transport growth: The quartz tube after the solid-phase reaction is completed is transferred to a dual-temperature zone tube furnace. The high-temperature zone temperature is set at 520-1020℃ and the low-temperature zone temperature is set at 450-720℃. After heating and holding, it is naturally cooled. The crystal grows in the low-temperature zone through the action of iodine transport agent. S5. Post-treatment: The grown crystals are ultrasonically cleaned in anhydrous ethanol and then annealed under vacuum at 150-220℃ to remove residual iodine.

5. The method according to claim 4, characterized in that, The high vacuum condition mentioned in step S2 is not less than 2.5 × 10⁻⁶. -2 Pa.

6. The method according to claim 4, characterized in that, The conditions for the swinging motion described in step S3 are: swing angle ±15°, rotation speed 24-70 r / min.

7. The method according to claim 4, characterized in that, The heat preservation time in step S4 shall not exceed 7200 min.

8. The method according to claim 4, characterized in that, The ultrasonic cleaning time in step S5 is 10-30 minutes, and the annealing condition is a vacuum degree not exceeding 3 × 10⁻⁶. -3 Pa, annealing time is 60-120 min.

9. An optoelectronic device, characterized in that, It includes the ternary compound semiconductor crystals of the IIIA-VA-VIA group as described in any one of claims 1-3.

10. The application of the IIIA-VA-VIA group ternary compound semiconductor crystal as described in any one of claims 1-3 or the optoelectronic device as described in claim 9 in polarization detection, encrypted communication, optoelectronic sensors or integrated optoelectronic devices.

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