CN105236482A - A Quaternary Sulfur Antimony Compound ACuSb2S4 Semiconductor Material - Google Patents

Abstract

The invention discloses a quaternary sulfur antimony compound ACuSb ₂ S ₄ semiconductor material. The quaternary sulfur-antimony compound of the present invention has a chemical composition formula of ACuSb ₂ S ₄ , wherein A is one of the alkali metal cations Rb and Cs that balance the anion skeleton. Its specific preparation process includes: weighing an appropriate amount of alkali metal hydroxide, copper elemental substance, antimony powder, and sulfur powder in a ratio of 1:2:0.5:2, using hydrazine hydrate and polyethylene glycol as solvents, and React at 160°C for 7 days to obtain black-red blocky crystals. The method has the advantages of simple operation process, low cost of raw materials, mild reaction conditions and the like. The quaternary sulfur-antimony compound obtained by this method belongs to the monoclinic system, C2/c (No.15) space group, has a new three-dimensional open framework structure, and has an energy band of about 1.7eV. It is a narrow bandgap semiconductor material and can be used for the preparation of optical semiconductor devices.

Description

A quaternary sulfur antimony compound ACuSb2S4 semiconductors

technical field

The invention relates to a quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material, which belongs to the field of inorganic semiconductor materials.

Background technique

With the rapid development of global science and technology, the world today has entered the electronic information age. Semiconductor materials are the matrix materials that constitute many solid-state electronic devices, and have important applications in optical communication equipment, information storage, processing, processing and display, such as semiconductor lasers and diodes. Semiconductor integrated circuits, semiconductor memory and photodiodes, etc. It is an indispensable functional material for energy, information, aerospace, and electronic technology, and occupies an extremely important position in electronic information materials. The development level of the semiconductor industry is one of the important symbols to measure the advanced level of a country.

Sulfur-antimony compounds have very complex structures, rich physical and chemical properties, and have potential application values in the fields of optoelectronic materials, molecular recognition and catalysis, ion exchange, nonlinear optical materials (NLO), chemical sensors, and semiconductors. One of the most studied inorganic multifunctional materials. Since the group V metal Sb(Ⅲ) ion contains stereochemically active 5S ² lone pair electrons, it forms the primary structural unit SbS _x (x=3,4,5) with S element. In an alkaline environment, the primary structural units SbS _x polymerize with each other to form polyanions, and then coordinate metal ions to regulate the geometric structure of the material and enrich the physical and chemical properties.

Since this century, middle and low temperature solvothermal synthesis methods have received more and more attention in solid-state chemical synthesis. Solvothermal reaction is an effective method for the synthesis of sulfur antimony compounds. The solvothermal synthesis system is generally in a non-ideal equilibrium state. Under high temperature and high pressure, the solvent of the synthesis reaction is in a critical or near-critical state, and the physical and chemical properties of the reactants in the solvent change greatly, which makes the thermochemical reaction of the solvent greatly different. In the normal state, the functional materials or crystals synthesized from this have their own excellent characteristics in terms of performance. However, because the reaction is difficult to control in a hydrothermal tank, the reproducibility of the reaction is not good. According to the researchers' many years of practice, the solvothermal synthesis method is mainly affected by the following factors: 1) polarity, viscosity, and critical temperature of the solvent, 2) reaction temperature, 3) cation radius, 4) reaction time, etc. By controlling the solvothermal reaction process, the purpose of optimizing experiments and preparing new products is achieved.

So far, only four quaternary sulfur antimony compounds A-Cu-Sb-S (A=Na, K, Rb, Cs) have been synthesized. In 1996, JE Jerome and JW Kolis et al synthesized Na ₂ CuSbS ₃ by supercritical ethylenediamine (JE Jerome, JW Kolis, et al. Eur. J. Solid State Inorg. Chem., 33 , 765 ( 1996).), is the first reported quaternary sulfur antimony compound A-Cu-Sb-S (A=Na, K, Rb, Cs); in 2005, B. Deng and JA Ibers et al. K ₂ CuSbS ₃ was obtained by the method (B. Deng, JA Ibers, et al. J. Solid State Chem., 178 , 3169 (2005).). Recently, YL An et al. successfully synthesized Rb ₂ Cu ₂ Sb ₂ S ₅ and Cs ₂ Cu ₂ Sb ₂ S ₅ using a solvothermal method (YL An, et al. Inorg. Chem., 53 , 4856 (2014). ). However, the microscopic spatial structures of these four compounds are all two-dimensional layered. In the quaternary system A-Cu-Sb-S (A=Na, K, Rb, Cs), there is no one-dimensional and three-dimensional crystal structure. Therefore, finding suitable reaction conditions, developing quaternary sulfur-antimony compound semiconductor materials with novel structures and appropriate energy gaps, and preparing optical semiconductor devices such as solar cell transition layer materials are of great practical significance for the development of semiconductor optoelectronics and other related industries.

Contents of the invention

The purpose of the present invention is to solve the problems existing in the prior art and provide a quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material. The specific technical scheme is as follows:

A quaternary sulfur-antimony compound ACuSb ₂ S ₄ The chemical composition formula of the quaternary sulfur-antimony compound in the semiconductor material is ACuSb ₂ S ₄ , wherein A is one of the alkali metal cations Rb and Cs.

The quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material belongs to monoclinic system, C2/c (No.15) space group, and has a three-dimensional open framework structure.

The energy gap of the quaternary sulfur antimony compound ACuSb ₂ S ₄ semiconductor material is 1.70eV.

Another object of the present invention is to provide a kind of preparation method of described quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material, the specific preparation process is as follows: Weigh the alkali whose amount ratio is 1:2:0.5:2 Metal hydroxide, copper element, antimony powder and sulfur powder are dissolved in hydrazine hydrate and polyethylene glycol as solvents, reacted at 160°C for 7 days, cooled, and then washed twice with distilled water and ethanol respectively. A quaternary sulfur-antimony compound semiconductor material is obtained; wherein the alkali metal hydroxide is RbOH or CsOH.

The mixing ratio of the hydrazine hydrate and polyethylene glycol is 1:4.

Another object of the present invention is to provide the quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material for preparing optical semiconductor devices.

Compared with the prior art, the present invention has the following beneficial effects: the present invention is prepared by a one-step solvothermal method, has the advantages of simple operation process, low cost of raw materials, mild reaction conditions and the like. The quaternary sulfur-antimony compound obtained by this method belongs to the monoclinic system, C2/c (No.15) space group, has a three-dimensional open framework structure, and has an energy band of about 1.7eV. It is a narrow bandgap semiconductor material and can be used in Fabrication of optical semiconductor devices.

Description of drawings

Figure 1(a) is the crystal morphology diagram of the semiconductor material RbCuSb ₂ S ₄ ;

Figure 1(b) is the crystal morphology diagram of the semiconductor material CsCuSb ₂ S ₄ ;

Figure 2(a) is the EDS spectrum of the semiconductor material RbCuSb ₂ S ₄ ;

Figure 2(b) is the EDS spectrum of the semiconductor material CsCuSb ₂ S ₄ ;

Figure 3(a) is the X-ray powder diffraction pattern and single crystal simulation diffraction pattern of the semiconductor material RbCuSb ₂ S ₄ , the abscissa represents the diffraction angle, and the ordinate represents the intensity;

Figure 3(b) is the X-ray powder diffraction pattern and single crystal simulation diffraction pattern of the semiconductor material CsCuSb ₂ S ₄ , the abscissa represents the diffraction angle, and the ordinate represents the intensity;

Fig. 4 is the single crystal structure figure of semiconductor material RbCuSb ₂ S ₄ molecule;

Figure 5(a) is the solid-state ultraviolet-visible absorption spectrum of the semiconductor material RbCuSb ₂ S ₄ , the abscissa indicates the wavelength, and the ordinate indicates the absorbance;

Figure 5(b) is the solid-state UV-visible absorption spectrum of the semiconductor material CsCuSb ₂ S ₄ , the abscissa represents the wavelength, and the ordinate represents the absorbance;

Figure 6(a) is the thermal analysis curve of the semiconductor material RbCuSb ₂ S ₄ , the abscissa indicates the temperature, and the ordinate indicates the weight percentage;

Figure 6(b) is the thermal analysis curve of the semiconductor material CsCuSb ₂ S ₄ , the abscissa indicates the temperature, and the ordinate indicates the weight percentage.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

The chemical composition formula of the quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material is ACuSb ₂ S ₄ , where A is one of the alkali metal cations Rb and Cs that balance the anion skeleton.

The quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material belongs to the monoclinic system, C2/c (No.15) space group, and has a new three-dimensional open framework structure.

The preparation method of the quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material is: Weigh an appropriate amount of alkali metal hydroxide, copper element, antimony powder, and sulfur powder with a ratio of 1:2:0.5:2 to hydrate Hydrazine and polyethylene glycol are used as solvents, reacted at 160°C for 7 days, cooled, and then washed twice with distilled water and ethanol respectively to obtain a quaternary sulfur-antimony compound semiconductor material; wherein the alkali metal hydroxide is RbOH or CsOH.

In the above preparation method, the mixing ratio of hydrazine hydrate and polyethylene glycol is 1:4.

The quaternary sulfur antimony compound ACuSb ₂ S ₄ semiconductor material has an energy gap of about 1.70eV, is a narrow band gap semiconductor material, and can be used to prepare optical semiconductor devices, which are solar cell transition layer materials.

In the present invention, unless otherwise specified, all equipment and raw materials are directly purchased from the market without further processing. The methods in the following examples, unless otherwise specified, are conventional methods in the art.

Example 1 :

RbCuSb ₂ S ₄ crystal:

Weigh the initial raw materials RbOH 1.0 mmol (0.103g), Cu 2.0 mmol (0.128g), Sb ₂ S ₃ 0.5 mmol (0.170g) and S 2.0 mmol (0.064g) into a hydrothermal kettle, then add hydrazine hydrate 0.5 mL and 2.0 mL of polyethylene glycol, and the reaction was carried out at 160 °C for 7 days in a hydrothermal kettle. After the reaction, open the hydrothermal kettle, take out the product, and wash twice with distilled water and absolute ethanol respectively to obtain black-red block crystals with a yield of 70% (based on copper) and a grain size of 200*300 μm (See Figure 1a). According to single crystal X-ray diffraction analysis, the crystal composition formula is RbCuSb ₂ S ₄ , which belongs to the monoclinic crystal system, and the space group is C2/c (No.15), a=7.3272(6) Å, b=11.1628(8) Å, c=10.7849(8) Å, α=90°, β=105.748(8)°, γ=90°, Z=4, V=849.01(11) Å ³ , the crystal structure is shown in 4. EDX elemental analysis shows that the crystal contains only four elements: Rb, Cu, Sb, and S, and the content ratio of each element is consistent with the result of single crystal diffraction analysis (see Figure 2 a). The crystals obtained by XRD analysis are phase-pure and consistent with the theoretical results (see Figure 3a). The energy gap of semiconductor material measured by UV-vis spectrum is 1.71 eV (see Figure 5 a). The TG spectrum shows that the semiconductor material has excellent thermal stability and does not decompose up to 500 °C (see Figure 6 a).

Example 2 :

CsCuSb ₂ S ₄ crystal:

Weigh the initial raw materials CsOH 1.0 mmol (0.150g), Cu 2.0 mmol (0.128g), Sb ₂ S ₃ 0.5 mmol (0.170g) and S 2.0 mmol (0.064g) into a hydrothermal kettle, then add hydrazine hydrate 0.5 mL and 2.0 mL of polyethylene glycol, and the reaction was carried out at 160 °C for 7 days in a hydrothermal kettle. After the reaction was over, the hydrothermal kettle was opened, the product was taken out, and the product was washed twice with distilled water and absolute ethanol respectively to obtain black-red block crystals with a yield of 58% (based on copper) and a grain size of 250*300 μm ( See Figure 1 b). According to single crystal X-ray diffraction analysis, the crystal composition formula is CsCuSb ₂ S ₄ , which belongs to the monoclinic crystal system, and the space group is C2/c (No.15), a=7.5859(7) Å, b=11.1225(9) Å, c=10.8286(10) Å, α=90°, β=105.364(9)°, γ=90°, Z=4, V=881.00(14) Å ³ . EDX elemental analysis shows that the crystal contains only four elements: Cs, Cu, Sb, and S, and the content ratio of each element is consistent with the result of single crystal diffraction analysis (see Figure 2 b). The crystals obtained by XRD analysis are phase-pure and consistent with the theoretical results (see Figure 3b). The energy gap of the semiconductor material measured by UV-vis spectrum is 1.70 eV (see Figure 5 b). The TG spectrum shows that the semiconductor material has excellent thermal stability and does not decompose up to 500 °C (see Figure 6 b).

Claims (6)

1. A quaternary sulfur antimony compound ACuSb ₂ S ₄ semiconductor material, characterized in that the chemical composition formula of the quaternary sulfur antimony compound is ACuSb ₂ S ₄ , wherein A is one of alkali metal cations Rb and Cs. 2. a kind of quaternary sulfur antimony compound ACuSb ₂ S ₄ semiconductor material as claimed in claim 1, is characterized in that, described quaternary sulfur antimony compound ACuSb ₂ S ₄ semiconductor material belongs to monoclinic system, C2/c (No.15) space group with a three-dimensional open framework structure. 3 . The quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material according to claim 1 , wherein the energy gap of the quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material is 1.70 eV. 4. A preparation method of quaternary sulfur-antimony compound ACuSb ₂ S ₄ semiconductor material as claimed in claim 1, characterized in that: the ratio of the amount of substance taken is 1:2:0.5:2 alkali metal hydroxide Substance, copper element, antimony powder and sulfur powder are dissolved in hydrazine hydrate and polyethylene glycol as solvents, reacted at 160°C for 7 days, cooled, and washed twice with distilled water and ethanol respectively to obtain quaternary Sulfur-antimony compound semiconductor material; the alkali metal hydroxide is RbOH or CsOH. 5. the preparation method as claimed in claim 4 is characterized in that: the mixing ratio of described hydrazine hydrate and polyethylene glycol is 1:4. 6. The use of the quaternary sulfur antimony compound ACuSb ₂ S ₄ semiconductor material as claimed in claim 1, characterized in that it is used for preparing optical semiconductor devices.