A quaternary tin chalcogenide compound, a method for preparing the same and use thereof

Abstract

The application discloses a quaternary tin chalcogenide compound and a preparation method and application thereof, and belongs to the technical field of semiconductor materials. The novel quaternary tin chalcogenide compound disclosed by the application has a structure in which transition metal Cd and Sn form a tetrahedral coordination with S respectively, the tetrahedral SnS4 and the tetrahedral CdS4 are connected through edge sharing to form an anion layer, the layers are also connected through edge sharing of the tetrahedral SnS4 and the tetrahedral CdS4 to form a three-dimensional open framework, and alkali metal ions Na + balance the compound charge as a balance cation. The Sn and Cd metal atoms are located on the crystallographic mirror surface, and the coordination polyhedron, i.e. the MS4 tetrahedron, is mirror image disordered in two directions. When the compound is used as an optical material, the photocurrent under simulated sunlight is 0.2 mu A / cm 2 , and the compound has potential application value in the optical aspect.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor materials technology, specifically relating to a quaternary tin chalcogenide compound, its preparation method, and its application. Background Technology

[0002] Polychalcogenides, due to their rich composition and diverse structures, possess a wide range of physicochemical properties, such as electrical, optical, and magnetic properties. Therefore, these compounds have broad application prospects in modern scientific fields such as nonlinear optics, photocatalysis, ion exchange, and photoelectrochemical cells. The synthesis and research of polychalcogenides has become an important area of ​​inorganic non-chemical synthesis.

[0003] In recent decades, significant progress has been made in the synthesis of polychaetes. A large number of chaetes have been synthesized using high-temperature solid-state methods, medium-temperature fluxing methods, and low-temperature solvent methods, greatly enriching the research field of polychaetes. The solvothermal method, due to its advantages such as high synthesis yield, simple process and equipment, good operability and tunability, mild reaction conditions, and low synthesis temperature, is widely used in the crystal synthesis of chaetes.

[0004] Sn, a Group 14 element, possesses diverse coordination modes and a wide range of bond lengths and angles, enabling it to coordinate with chalcogenides (Q = S, Se, Te) to form SnQ4 tetrahedral, SnQ5 trigonal bipyramidal, and SnQ6 octahedral configurations. These configurations interconnect through a series of self-condensation mechanisms, forming diverse structural units. These structural units are linked by chalcogenides (Q = S, Se, Te) to form different dimensional (one-dimensional, two-dimensional, and three-dimensional) structural types. Simultaneously, tin sulfides can combine with other transition metals from other Group 14 elements to form more anionic layers, thereby constructing a large number of novel multi-component tin sulfide compounds through different coordination polyhedral combinations.

[0005] In recent years, scholars both at home and abroad have synthesized many tin chalcogenides using the solvothermal method, such as [Mn(tren)]2Sn2S6 and [Eu2(tepa)2(μ-OH)2(μ-Sn2S6)](tepa). 0.5 H₂O, [La(dien)₃]₂[Sn₂S₆]Cl₂, etc. Due to its strong reducing properties, the introduction of Sn into complex synthetic conditions is quite difficult, and its single-element composition also hinders the flexible control of its photoelectric properties, limiting the development of Sn-based chalcogenides. Enabling them to fully utilize their excellent properties in existing scientific fields has become a focus of related research. Summary of the Invention

[0006] In order to overcome the shortcomings of the prior art, the present invention aims to provide a quaternary tin chalcogenide compound, its preparation method and application, so as to solve the problem of the difficulty in introducing Sn element and enrich the chemical structure of tin-based chalcogenide compounds.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] This invention discloses a quaternary tin sulfide compound with the chemical formula Na2CdSnS3.

[0009] Furthermore, the Na₂CdSnS₃ belongs to the orthorhombic crystal system of space group F₂₂, and its cell parameters are: α=90.00°, β=90.00°, γ=90.00°, Z = 2, Dc = 2.916 g / cm³ 3 .

[0010] Furthermore, the Na₂CdSnS₃ possesses the property [CdSnS₃]. 2- Anionic framework, Na + It exists in the channel as a balancing cation to compensate for the framework charge.

[0011] This invention also discloses a method for preparing the above-mentioned quaternary tin chalcogenide compound, comprising the following steps:

[0012] Sodium hydroxide, cadmium powder, tin sulfide and elemental sulfur are mixed in a solvent and subjected to a hydrothermal reaction to obtain the reaction product.

[0013] The reaction product was washed to obtain a quaternary tin sulfide compound;

[0014] The molar ratio of sodium hydroxide, cadmium powder, tin sulfide and elemental sulfur is (1-2):(1-2):(0.5-1):(2-2.5).

[0015] Furthermore, the solvent is a mixture of PEG-400 and triethylenetetramine.

[0016] Further, the volume ratio of PEG-400 to triethylenetetramine is (1.0-2.0):(0.5-1).

[0017] Furthermore, the hydrothermal reaction is carried out at a temperature of 140–160°C for 6–10 days.

[0018] Furthermore, the washing process involves using distilled water and anhydrous ethanol.

[0019] The present invention also discloses the application of the above-mentioned tetroxide compound as an optical material.

[0020] Furthermore, when the quaternary tin chalcogenide compound is used as an optical material, the photocurrent under simulated sunlight is 0.2 μA / cm. 2 .

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] This invention discloses a quaternary tin sulfide compound, a novel sulfate containing transition metals. In its structure, transition metals Cd and Sn form tetrahedral coordination with S, respectively. Tetrahedral SnS4 and tetrahedral CdS4 are connected by edge sharing to form an anionic layer. The layers are also connected by edge sharing between tetrahedral SnS4 and tetrahedral CdS4 to form a three-dimensional open framework. The alkali metal ion Na... + As balancing cations, they balance the charge of the compound. Both Sn and Cd metal atoms are located on crystallographic mirrors, and their coordination polyhedra, i.e., MS4 tetrahedra, exhibit mirror-image disorder in two directions. This invention is successful.

[0023] This invention also discloses a method for preparing the aforementioned quaternary tin chalcogenide compound. The material synthesized by this method exhibits good thermal stability and chemical resistance. The use of a non-aqueous solvent greatly expands the range of selectable raw materials, resulting in low raw material costs. Due to the low boiling point of the organic solvent, a higher gas pressure can be achieved under the same conditions than hydrothermal synthesis, which is beneficial for crystal crystallization. Furthermore, the reaction conditions are mild, and the raw material costs are low.

[0024] This invention also discloses the application of quaternary tin sulfide compounds as optical materials. The quaternary tin sulfide compound optical materials prepared using this method can achieve a yield of ~50%. According to relevant experimental results, the photocurrent of the material under simulated sunlight is 0.2 μA / cm. 2 It has potential applications in optics. Attached Figure Description

[0025] Figure 1 The image shows the crystal morphology of Na2CdSnS3 prepared in this invention.

[0026] Figure 2 The EDS spectrum of the Na2CdSnS3 crystal prepared in this invention;

[0027] Figure 3 The structural diagram of Na2CdSnS3 prepared in this invention is shown.

[0028] Figure 4 The PXRD pattern and single-crystal simulated diffraction pattern of Na2CdSnS3 prepared in this invention are shown below.

[0029] Figure 5The photoelectric response test and analysis spectrum of the Na2CdSnS3 crystal prepared in this invention is shown. Detailed Implementation

[0030] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0031] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0032] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0033] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0034] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0035] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0036] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0037] Example 1

[0038] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0039] Weigh out 2 mmol (0.08 g) of initial raw materials NaOH, 2 mmol (0.224 g) of Cd, 1 mmol (0.151 g) of SnS and 2.5 mmol (0.08 g) of elemental S and place them in a hydrothermal reactor. Add 1 mL of triethylenetetramine and 2 mL of PEG-400. Place the hydrothermal reactor in a drying oven and react at 160 °C for 7 days. Wash the product twice with deionized water and anhydrous ethanol, respectively. The resulting pale yellow octahedral blocky crystals are a quaternary tin sulfide compound (Na2CdSnS3).

[0040] The Na2CdSnS3 crystal morphology diagram in this embodiment is as follows: Figure 1 As shown. Figure 2 EDS elemental analysis showed that the crystal contained four elements: Na, Cd, Sn, and S.

[0041] Example 2

[0042] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0043] Weigh out 2 mmol (0.08 g) of initial raw materials NaOH, 2 mmol (0.224 g) of Cd, 1 mmol (0.151 g) of SnS, and 2.5 mmol (0.08 g) of elemental S and place them in a hydrothermal reactor. Add 1 mL of diethylenetriamine and place the reactor in a drying oven at 140 °C for 7 days. Wash the product twice with distilled water and anhydrous ethanol, respectively. A pale yellow octahedral blocky crystal, a quaternary tin sulfide compound Na2CdSnS3, is obtained. The morphology of its crystal is shown in the image below. Figure 1 similar.

[0044] Example 3

[0045] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0046] Weigh out 2 mmol (0.08 g) of initial raw materials NaOH, 2 mmol (0.224 g) of Cd, 1 mmol (0.151 g) of SnS, and 2.5 mmol (0.08 g) of elemental S and place them in a hydrothermal reactor. Add 1 mL of ethylenediamine and place the reactor in a drying oven at 140 °C for 6 days. Wash the product twice with distilled water and anhydrous ethanol, respectively. Pale yellow octahedral blocky crystals, i.e., the quaternary tin sulfide compound Na2CdSnS3, are obtained. The morphology of its crystals is shown in the figure below. Figure 1 similar.

[0047] Example 4

[0048] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0049] Weigh out 1 mmol (0.04 g) of initial raw materials NaOH, 1 mmol (0.112 g) of Cd, 0.5 mmol (0.0755 g) of SnS, and 2 mmol (0.064 g) of elemental S and place them in a hydrothermal reactor. Then add 0.5 mL of triethylenetetramine and 1 mL of PEG-400. Place the hydrothermal reactor in a drying oven and react at 140 °C for 10 days. Wash the product twice with distilled water and anhydrous ethanol, respectively. Pale yellow octahedral blocky crystals, namely the quaternary tin sulfide compound Na2CdSnS3, are obtained. The morphology of its crystals is shown in the figure. Figure 1 similar.

[0050] Example 5

[0051] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0052] Weigh out 1 mmol (0.04 g) of initial raw materials NaOH, 1 mmol (0.112 g) of Cd, 0.5 mmol (0.0755 g) of SnS, and 2 mmol (0.064 g) of elemental S and place them in a hydrothermal reactor. Then add 1 mL of triethylenetetramine, 2 mL of PEG-400, and 0.3 mL of ammonia. Place the hydrothermal reactor in a drying oven and react at 160 °C for 10 days. Wash the product twice with distilled water and anhydrous ethanol, respectively. The quaternary tin sulfide compound Na2CdSnS3 is obtained. The morphology of its crystals is shown in the figure. Figure 1 similar.

[0053] Example 6

[0054] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0055] Weigh out 1 mmol (0.04 g) of initial raw materials NaOH, 1 mmol (0.112 g) of Cd, 0.5 mmol (0.0755 g) of SnS and 2 mmol (0.064 g) of elemental S and place them in a hydrothermal reactor. Then add 1 mL of ethylenediamine, 2 mL of PEG-400 and 0.3 mL of ammonia. Place the hydrothermal reactor in a drying oven and react at 160 °C for 10 days. Wash the product twice with distilled water and anhydrous ethanol, respectively.

[0056] Example 7

[0057] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0058] Weigh out 2 mmol (0.04 g) of initial raw materials NaOH, 2 mmol (0.112 g) of Cd, 1 mmol (0.0755 g) of SnS and 2 mmol (0.064 g) of elemental S and place them in a hydrothermal reactor. Then add 2 mL of ethylenediamine, 1 mL of PEG-400 and 0.3 mL of ammonia. Place the hydrothermal reactor in a drying oven and react at 160 °C for 10 days. Wash the product twice with distilled water and anhydrous ethanol, respectively.

[0059] Example 8

[0060] A method for preparing a quaternary tin chalcogenide compound includes the following steps:

[0061] Weigh out 2 mmol (0.04 g) of initial raw materials NaOH, 2 mmol (0.112 g) of Cd, 1 mmol (0.0755 g) of SnS and 2 mmol (0.064 g) of elemental S and place them in a hydrothermal reactor. Then add 2 mL of ethylenediamine, 1 mL of PEG-400 and 0.3 mL of ammonia. Place the hydrothermal reactor in a drying oven and react at 160 °C for 8 days. Wash the product twice with distilled water and anhydrous ethanol, respectively.

[0062] The crystals prepared in Example 1 were selected under an optical microscope. A single crystal of the chalcogenide compound Na₂CdSnS₃ of suitable size was selected for X-ray diffraction. The results showed that Na₂CdSnS₃ belongs to the orthorhombic crystal system of space group F₂₂, and its cell parameters are as follows: α=90.00°, β=90.00°, γ=90.00°, Z = 2, D c =2.916g / cm 3 The molecular structure obtained by analysis is as follows: Figure 3 As shown. A series of performance tests were performed on the crystalline powder of the chalcogenide compound. After the sample was ground uniformly, X-ray powder diffraction was performed on the crystalline powder. The powder diffraction pattern of the compound was basically consistent with the diffraction pattern obtained from the single crystal structure calculation, such as... Figure 4As shown. The photocurrent response of the compound was tested by applying a bias potential of 0.2V, and it responded to light illumination. The photocurrent response spectrum is shown below. Figure 5 As shown, the photoelectric response is fast and stable, with a current density difference of approximately 0.2 μA / cm² per response. 2 The rapid separation of photogenerated electrons and holes, and such high electron transport efficiency, may be attributed to [CdSnS3] in Na2CdSnS3. 2- With its highly interconnected open frame, the separation and recombination can maintain dynamic equilibrium and retain a small signal fluctuation within 25 seconds, making it an excellent optical device.

[0063] 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 quaternary tin chalcogenide compound, characterized in that, The chemical formula of the quaternary tin sulfide compound is Na₂CdSnS₃.

2. The quaternary tin chalcogenide compound according to claim 1, characterized in that, The Na₂CdSnS₃ belongs to the orthorhombic crystal system of space group F₂22, and its cell parameters are: a = 9.3964 Å, b = 9.3236(7) Å, c = 9.3223(8) Å, α = 90.00°, β = 90.00°, γ = 90.00°, V = 816.71(3) Å. 3 Z=2, Dc=2.916g / cm 3 .

3. The quaternary tin sulfide compound according to claim 2, characterized in that, The Na₂CdSnS₃ possesses the property [CdSnS₃]. 2- Anionic framework, Na + It exists in the channel as a balancing cation to compensate for the framework charge.

4. The method for preparing the quaternary tin chalcogenide compound according to any one of claims 1 to 3, characterized in that, Includes the following steps: Sodium hydroxide, cadmium powder, tin sulfide and elemental sulfur are mixed in a solvent and subjected to a hydrothermal reaction to obtain the reaction product. The reaction product was washed to obtain a quaternary tin sulfide compound; The molar ratio of sodium hydroxide, cadmium powder, tin sulfide, and elemental sulfur is (1~2):(1~2):(0.5~1):(2~2.5). The solvent is a mixture of PEG-400 and triethylenetetramine.

5. The method for preparing the quaternary tin chalcogenide compound according to claim 4, characterized in that, The volume ratio of PEG-400 to triethylenetetramine is (1.0~2.0):(0.5~1).

6. The method for preparing the quaternary tin chalcogenide compound according to claim 4, characterized in that, The hydrothermal reaction is carried out at a temperature of 140-160℃ for 6-10 days.

7. The method for preparing the quaternary tin chalcogenide compound according to claim 4, characterized in that, The washing process involves using distilled water and anhydrous ethanol.

8. The application of the quaternary tin chalcogenide compound according to any one of claims 1 to 3, characterized in that, The quaternary tin chalcogenide compound is used as an optical material.

9. The application of the quaternary tin chalcogenide compound according to claim 8, characterized in that, When the quaternary tin chalcogenide compound is used as an optical material, the photocurrent under simulated sunlight is 0.2 μA / cm. 2 .

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