Preparation method of antimony iodide crystal and thin film material
Through ultrasonic chemical reaction and two-stage temperature control method, antimony iodide crystals and films are prepared, which solves the problems of high purity requirements and complex process, and achieves efficient and environmentally friendly antimony iodide preparation, which is suitable for industrial production.
Patent Information
- Application Number
- CN202411270762.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-11
- Publication Date
- 2024-12-31
AI Technical Summary
The existing preparation methods for antimony iodide have problems such as high purity requirements for raw materials, complex processes, environmental pollution and inadequate for large-scale industrial production.
Precursor solutions are prepared in methanol, ethanol or isopropanol at a molar ratio of 1:1 to 1.5, antimony iodide powder is prepared by ultrasonic chemical reaction, and two-stage temperatures are performed in a tube furnace. Controlled high temperature sintering to prepare antimony iodide crystals or films.
It improves the preparation efficiency, reduces production costs, avoids environmental pollution, ensures the high purity and stability of the product, and is suitable for industrial production.
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Figure CN119221120A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of semiconductor materials, and in particular relates to a method for preparing antimony iodide crystal and thin film material. Background Art
[0002] Antimony iodide is an important dopant for semiconductors and thermoelectric materials, and can be used as a raw material for the preparation of catalysts in the chemical industry and in the pharmaceutical field. At present, the preparation methods of antimony iodide mainly adopt two methods: wet synthesis or dry synthesis.
[0003] The wet synthesis of antimony iodide uses benzene as a solvent, and reacts antimony powder with iodine by heating and refluxing. During the reaction, iodine is added in batches to control the reaction rate and avoid the danger caused by violent reactions. When most of the iodine is added, red antimony iodide crystals will precipitate. After the reaction is complete, hexagonal antimony iodide crystals can be obtained by cooling and crystallization. The wet synthesis process is complex and has a low yield. The use of benzene solvent causes environmental pollution, and the addition rate of iodine needs to be strictly controlled. In addition, the product is prone to contain water of crystallization, which affects the application of the product.
[0004] The dry synthesis of antimony iodide has attracted much attention because it does not require solvent, is environmentally friendly, and has a good yield. Dry synthesis is generally a chemical vapor deposition and sealed tube heating method. CN106335923B discloses "a method for preparing antimony iodide", the method is: iodine with a purity greater than 99.9% is placed in a clean glass tube sealed at one end, and then an antimony block with a purity greater than 99.99% is covered on the iodine, the total charge does not exceed 15% of the glass tube capacity, and the vacuum is evacuated to less than 15Pa and sealed; put it in a swing furnace at 320-380°C and heat for 2-12 hours, take it out after the reaction is completed, and cool it naturally to obtain an antimony iodide yield of 99% and a purity of 99.996%. However, the dry preparation requires high-purity (greater than 99.9%) raw materials, especially the high-purity antimony raw material has a high cost, and the dry synthesis requires vacuum sealing, harsh reaction conditions, cumbersome operation, and large equipment investment, which is not suitable for large-scale industrial production. Summary of the invention
[0005] The technical problem to be solved by the present invention is to provide a method for preparing antimony iodide crystals and thin film materials which has low requirements on the purity of raw antimony, is easy to obtain, has a simple process, mild reaction conditions, is easy to operate, and is suitable for industrial production.
[0006] The technical solution of the present invention is:
[0007] A method for preparing antimony iodide crystal and thin film material, the specific steps of which are as follows:
[0008] S1. Prepare precursor solution
[0009] The raw materials are elemental iodine and industrial-grade elemental antimony, the molar ratio of the elemental antimony to the elemental iodine is 1:1 to 1:1.5, and methanol, ethanol or isopropanol is used as a reaction solvent to obtain a precursor solution;
[0010] S2. Preparation of antimony iodide by sonochemical reaction
[0011] The precursor solution prepared in step S1 is subjected to ultrasonic reaction at room temperature and a power of 40 to 60 kW for 60 to 120 minutes, and then dried to obtain antimony iodide powder;
[0012] S3. Preparation of antimony iodide crystals / thin films
[0013] The antimony iodide powder of step S2 is placed in a container, and sintered at high temperature in a tube furnace at a vacuum degree of 0.5-5 Pa. The tube furnace is divided into two temperature zones, the temperature of temperature zone 1 is 200-260° C., and the temperature of temperature zone 2 is 50-150° C. Antimony iodide crystals / films are formed in the temperature zone 2 of the tube furnace;
[0014] When preparing antimony iodide crystals, the container is a quartz tube, the antimony iodide powder is placed near the bottom of the quartz tube, the bottom of the quartz tube is located at the temperature zone 1, and the quartz tube mouth is plugged with a quartz plug, and the reaction time is 2 to 5 hours;
[0015] When preparing antimony iodide film, the container is a quartz boat, and the quartz boat filled with antimony iodide powder is placed at the position of temperature zone 1; the substrate is placed at the position of temperature zone 2, and the reaction time is 3 to 15 minutes.
[0016] Furthermore, when preparing antimony iodide crystals, the upper middle portion of the quartz tube is located in temperature zone 2.
[0017] Furthermore, the purity of industrial-grade elemental antimony is ≥70%.
[0018] Furthermore, in step S1, the molar ratio of the elemental antimony to the elemental iodine is 1:1.5.
[0019] Furthermore, the purity of the elemental iodine is ≥95%, and the purity of the solvent is ≥98%.
[0020] Furthermore, in step S3, the substrate material is soda-lime glass, FTO or ITO.
[0021] The beneficial effects of the present invention are:
[0022] (1) Using elemental antimony and elemental iodine as raw materials, antimony iodide powder is prepared by a sonochemical method. The raw material purity requirement is low, and the yield is as high as 99%, which significantly improves the preparation efficiency.
[0023] (2) The entire preparation process is relatively simple and does not require complex equipment or high-purity raw materials, thereby reducing production costs. Whether it is small-scale laboratory preparation or large-scale production, it has high economic feasibility.
[0024] (3) Compared with the traditional wet synthesis process, the present invention avoids environmental pollution problems, such as the generation of wastewater and waste gas, and the problem of crystal water that may be contained in the wet synthesis product, and is safe and environmentally friendly.
[0025] (4) The two-stage temperature control is adopted, which can accurately control the sublimation, evaporation and crystallization / film formation process of antimony iodide, ensuring the stability and controllability of the preparation process. The antimony iodide crystals obtained by the sublimation method have high purity and crystallinity, ensuring the stability of material properties. The thin film prepared by vapor transport deposition has uniform composition, and the material thickness can be controlled by the sintering time in the tubular furnace to ensure product quality. Antimony iodide crystals and thin film materials can be widely used in semiconductors, optoelectronics and other fields. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is a schematic diagram of preparing antimony iodide crystals by sublimation method of the present invention, in which: 1 is a quartz plug, 2 is antimony iodide powder prepared by sonochemistry;
[0027] Figure 2 The schematic diagram of the preparation of antimony iodide thin film by the gas phase transport method of the present invention, in which: 1 is antimony iodide powder prepared by sonochemistry, 2 is an evaporation boat, and 3 is a substrate;
[0028] Figure 3 The antimony iodide powder prepared by the sonochemical method of the present invention (corresponding to Example 1) is shown in Figure (a) and a scanning electron microscope (SEM) image (b);
[0029] Figure 4 is an X-ray diffraction pattern (XRD) of antimony iodide powder prepared by sonochemical method of the present invention (corresponding to Example 1);
[0030] Figure 5 The optical microscope image (a) and the scanning electron microscope image (SEM) (b) of the antimony iodide crystal prepared by the sublimation method of the present invention (corresponding to Example 1);
[0031] Figure 6 This is the XRD pattern of antimony iodide crystals prepared by sublimation method of the present invention (corresponding to Example 1);
[0032] Figure 7 The antimony iodide thin film (a) and scanning electron microscope (b) of the FTO substrate prepared by the vapor transport method of the present invention (corresponding to Example 2);
[0033] Figure 8This is the XRD pattern of the antimony iodide thin film on the FTO substrate prepared by the vapor transport method of the present invention (corresponding to Example 2);
[0034] Fig. 9 It is the ultraviolet-visible absorption spectrum and Tauc diagram of the antimony iodide film prepared by the vapor transport method of the present invention (corresponding to Example 2). DETAILED DESCRIPTION
[0035] Example 1
[0036] (1) adding elemental antimony and elemental iodine into methanol at a molar ratio of 1:1.5, wherein the molar volume ratio of elemental antimony to methanol is 0.6 mol elemental antimony / 1 mL methanol, the purity of the elemental antimony is 70%, the purity of the elemental iodine is ≥95%, the purity of the solvent methanol is ≥98%, reacting at room temperature for 100 min under an ultrasonic power of 40 kW, and drying to obtain antimony iodide powder; Figure 4 This is the XRD pattern of antimony iodide powder after drying; from the XRD pattern, it can be seen that the final product prepared is antimony iodide;
[0037] (2) Figure 1 As shown, the antimony iodide powder prepared in step (1) is placed at the bottom of a quartz test tube, plugged with a quartz plug (not sealed), and placed in a dual-temperature zone tubular furnace. The vacuum degree of the tubular furnace is 5 Pa, and it is divided into two temperature zones. The temperature of temperature zone 1 is 240° C., and the temperature of temperature zone 2 is 100° C. The sealing end of the quartz plug is located in temperature zone 2. The reaction time is 4 hours to obtain antimony iodide crystals; Figure 5 : is the XRD diagram of the obtained antimony iodide crystals; from the XRD diagram, it can be seen that the final product prepared is antimony iodide, which has good crystallization, a (006) preferred orientation, no impurity peaks, and a purity of 99.9%.
[0038] Example 2
[0039] like Figure 2 As shown, the antimony iodide powder prepared in step (1) of Example 1 is placed in a quartz boat, and then placed in a dual-temperature zone tubular furnace. The vacuum degree of the tubular furnace is 5 Pa, and it is divided into two temperature zones. The temperature of temperature zone 1 is 200° C., and the temperature of temperature zone 2 is 50° C. The quartz boat is located in the middle of temperature zone 1, and the FTO substrate is placed in the middle of temperature zone 2. The reaction time is 3 min to obtain an antimony iodide film; Figure 7 (b) is a photo of the antimony iodide film. Figure 7 It can be seen that the film particles are of uniform size and have good uniformity; Figure 8 is the XRD pattern of the antimony iodide film. Figure 8 It can be seen that the prepared thin film product is antimony iodide, which has good crystallization and no impurity peaks. Fig. 9 (a) is the UV-visible absorption spectrum of the antimony iodide film, and it can be seen that its absorption edge is at 580nm. Fig. 9(b) is the Tauc plot of the antimony iodide film, from which it can be concluded that the band gap of the film is 2.14 eV, which is suitable for use in semiconductor devices.
[0040] Example 3
[0041] (1) adding elemental antimony and elemental iodine to methanol in a molar ratio of 1:1.5, wherein the molar volume ratio of elemental antimony to methanol is 0.5 mol elemental antimony / 1 mL methanol, the purity of the elemental antimony is 70%, the purity of the elemental iodine is ≥95%, the purity of the solvent methanol is ≥98%, reacting at room temperature for 80 min under an ultrasonic power of 60 kW, and drying to obtain antimony iodide powder;
[0042] (2) Figure 1 As shown, the antimony iodide powder prepared in step (1) is placed at the bottom of a quartz test tube, plugged with a quartz plug (not sealed), and placed in a dual-temperature zone tubular furnace. The vacuum degree of the tubular furnace is 5 Pa, and it is divided into two temperature zones. The temperature of temperature zone 1 is 220° C., and the temperature of temperature zone 2 is 100° C. The sealed end of the quartz plug is located in temperature zone 2. The reaction time is 3 hours to obtain antimony iodide crystals. The XRD pattern of the obtained antimony iodide crystals is similar to that of Example 1. The final product prepared is antimony iodide, which has good crystallization, is (006) preferred orientation, has no impurity peaks, and has a purity of 99.9%.
[0043] Example 4
[0044] like Figure 2 As shown, the antimony iodide powder prepared in step (1) of Example 3 was placed in a quartz boat, and then placed in a dual-temperature zone tube furnace. The vacuum degree of the tube furnace was 5 Pa, and it was divided into two temperature zones. The temperature of temperature zone 1 was 260°C, and the temperature of temperature zone 2 was 50°C. The quartz boat was located in the middle of temperature zone 1, and a soda-lime glass substrate was placed in the middle of temperature zone 2. The reaction time was 5 minutes to obtain an antimony iodide film. The scanning electron microscope image and XRD pattern of the obtained antimony iodide film were similar to those of Example 2. Figure 7 (b) and Figure 8 The final product is antimony iodide, which has good crystallization, no impurity peaks, and a purity of 99.9%. The antimony iodide film has consistent particle size and good uniformity.
[0045] Example 5
[0046] (1) adding elemental antimony and elemental iodine to ethanol in a molar ratio of 1:1.5, wherein the molar volume ratio of elemental antimony to ethanol is 0.3 mol elemental antimony / 1 mL ethanol, the purity of the elemental antimony is 70%, the purity of the elemental iodine is ≥95%, and the purity of the solvent ethanol is ≥98%, reacting at room temperature for 120 min under an ultrasonic power of 40 kW, and drying to obtain antimony iodide powder;
[0047] (2) Figure 1As shown, the antimony iodide powder prepared in step (1) is placed at the bottom of a quartz test tube, plugged with a quartz plug (not sealed), and placed in a dual-temperature zone tubular furnace. The vacuum degree of the tubular furnace is 5 Pa, and it is divided into two temperature zones. The temperature of temperature zone 1 is 200° C., and the temperature of temperature zone 2 is 50° C. The sealed end of the quartz plug is located in temperature zone 2. The reaction time is 5 h to obtain antimony iodide crystals. The XRD pattern of the obtained antimony iodide crystals is similar to that of Example 1. The final product prepared is antimony iodide, which has good crystallization, is (006) preferred orientation, does not have any impurity peaks, and has a purity of 99.9%.
[0048] Example 6
[0049] like Figure 2 As shown, the antimony iodide powder prepared in step (1) of Example 5 was placed in a quartz boat, and then placed in a dual-temperature zone tube furnace. The vacuum degree of the tube furnace was 5 Pa, and it was divided into two temperature zones. The temperature of temperature zone 1 was 240°C, and the temperature of temperature zone 2 was 80°C. The quartz boat was located in the middle of temperature zone 1, and the ITO substrate was placed in the middle of temperature zone 2. The reaction time was 4 minutes to obtain an antimony iodide film. The scanning electron microscope image and XRD pattern of the obtained antimony iodide film were similar to those of Example 2. Figure 7 (b) and Figure 8 The final product is antimony iodide, which has good crystallization, no impurity peaks, and a purity of 99.9%. The antimony iodide film has consistent particle size and good uniformity.
[0050] Example 7
[0051] (1) adding elemental antimony and elemental iodine to isopropanol in a molar ratio of 1:1.5, wherein the molar volume ratio of elemental antimony to isopropanol is 0.2 mol antimony / 1 mL isopropanol, the purity of the elemental antimony is 70%, the purity of the elemental iodine is ≥95%, the purity of the solvent isopropanol is ≥98%, reacting at room temperature for 60 min under an ultrasonic power of 60 kW, and drying to obtain antimony iodide powder;
[0052] (2) Figure 1 As shown, the antimony iodide powder prepared in step (1) is placed at the bottom of a quartz test tube, plugged with a quartz plug (not sealed), and placed in a dual-temperature zone tubular furnace. The vacuum degree of the tubular furnace is 5 Pa, and it is divided into two temperature zones. The temperature of temperature zone 1 is 260°C, and the temperature of temperature zone 2 is 120°C. The sealing end of the quartz plug is located in temperature zone 2. The reaction time is 2 hours to obtain antimony iodide crystals. The XRD pattern of the obtained antimony iodide crystals is similar to that of Example 1. The final product prepared is antimony iodide, which has good crystallization, is (006) preferred orientation, has no impurity peaks, and has a purity of 99.9%.
[0053] Example 8
[0054] like Figure 2As shown, the antimony iodide powder prepared in step (1) of Example 7 was placed in a quartz boat, and then placed in a dual-temperature zone tube furnace. The vacuum degree of the tube furnace was 5 Pa, and it was divided into two temperature zones. The temperature of temperature zone 1 was 220°C, and the temperature of temperature zone 2 was 100°C. The quartz boat was located in the middle of temperature zone 1, and a soda-lime glass substrate was placed in the middle of temperature zone 2. The reaction time was 15 minutes to obtain an antimony iodide film. The scanning electron microscope image and XRD pattern of the obtained antimony iodide film were similar to those of Example 2. Figure 7 (b) and Figure 8 The final product is antimony iodide, which has good crystallization, no impurity peaks, and a purity of 99.9%. The antimony iodide film has consistent particle size and good uniformity.
[0055] Comparative Example 1 is a parallel experiment of Example 1, except that the ultrasonic-assisted treatment is replaced by stirring, and the rest is the same as Example 1.
[0056] (1) adding elemental antimony and elemental iodine to methanol in a molar ratio of 1:1.5, wherein the molar volume ratio of elemental antimony to methanol is 0.6 mol elemental antimony / 1 mL methanol, the purity of the elemental antimony is 70%, the purity of the elemental iodine is ≥95%, the purity of the solvent methanol is ≥98%, reacting at room temperature for 100 minutes under stirring conditions, and drying to obtain a mixed powder;
[0057] (2) Place the mixed powder prepared in step (1) at the bottom of a quartz test tube, plug it with a quartz plug (not sealed), and place it in a dual-temperature zone tubular furnace. The vacuum degree of the tubular furnace is 5 Pa and it is divided into two temperature zones. The temperature of temperature zone 1 is 240°C and the temperature of temperature zone 2 is 100°C. The sealed end of the quartz plug is located in temperature zone 2. The reaction time is 4 hours.
[0058] Comparative Example 2 is a parallel experiment of Example 2, except that the ultrasonic-assisted treatment is replaced by stirring, and the rest is the same as Example 2.
[0059] (1) adding elemental antimony and elemental iodine to methanol in a molar ratio of 1:1.5, wherein the molar volume ratio of elemental antimony to methanol is 0.6 mol elemental antimony / 1 mL methanol, the purity of the elemental antimony is 70%, the purity of the elemental iodine is ≥95%, the purity of the solvent methanol is ≥98%, reacting at room temperature for 100 minutes under stirring conditions, and drying to obtain a mixed powder;
[0060] (2) placing the mixed powder prepared in step (1) in a quartz boat, and placing it in a dual-temperature zone tube furnace. The vacuum degree of the tube furnace is 5 Pa, and it is divided into two temperature zones. The temperature of temperature zone 1 is 200° C., and the temperature of temperature zone 2 is 50° C. The quartz boat is located in the middle of temperature zone 1, and the FTO substrate is placed in the middle of temperature zone 2. The reaction time is 3 min;
[0061] Comparative Examples 1 and 2 do not use sonochemical reaction to prepare antimony iodide. Ordinary stirring is used. It is difficult for elemental antimony and elemental iodine to react. The obtained mixed powder is placed in a dual-temperature zone tubular furnace. After heating, iodine will volatilize quickly, and only a very small amount of antimony participates in the reaction, and no antimony iodide crystals / films can be obtained.
[0062] The above are only specific embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for preparing antimony iodide crystal and thin film material, characterized in that: The specific steps are as follows: S1. Prepare precursor solution The raw materials are elemental iodine and industrial-grade elemental antimony, the molar ratio of the elemental antimony to the elemental iodine is 1:1 to 1:1.5, and methanol, ethanol or isopropanol is used as a reaction solvent to obtain a precursor solution; S2. Preparation of antimony iodide by sonochemical reaction The precursor solution prepared in step S1 is subjected to ultrasonic reaction at room temperature and a power of 40 to 60 kW for 60 to 120 minutes, and then dried to obtain antimony iodide powder; S3. Preparation of antimony iodide crystals / thin films The antimony iodide powder of step S2 is placed in a container, and sintered at high temperature in a tube furnace at a vacuum degree of 0.5-5 Pa. The tube furnace is divided into two temperature zones, the temperature of temperature zone 1 is 200-260° C., and the temperature of temperature zone 2 is 50-150° C. Antimony iodide crystals / films are formed in the temperature zone 2 of the tube furnace; When preparing antimony iodide crystals, the container is a quartz tube, the antimony iodide powder is placed near the bottom of the quartz tube, the bottom of the quartz tube is located at the temperature zone 1, and the quartz tube mouth is plugged with a quartz plug, and the reaction time is 2 to 5 hours; When preparing antimony iodide film, the container is a quartz boat, and the quartz boat filled with antimony iodide powder is placed at the position of temperature zone 1; the substrate is placed at the position of temperature zone 2, and the reaction time is 3 to 15 minutes.
2. The method for preparing antimony iodide crystal and thin film material according to claim 1, characterized in that: When preparing antimony iodide crystals, the upper middle portion of the quartz tube is located in temperature zone 2.
3. The method for preparing antimony iodide crystal and thin film material according to claim 1, characterized in that: The purity of industrial-grade elemental antimony is ≥70%.
4. The method for preparing antimony iodide crystal and thin film material according to claim 1, characterized in that: In step S1, the molar ratio of the elemental antimony to the elemental iodine is 1:1.
5.
5. The method for preparing antimony iodide crystal and thin film material according to claim 1, characterized in that: The purity of the elemental iodine is ≥95%, and the purity of the solvent is ≥98%.
6. The method for preparing antimony iodide crystal and thin film material according to claim 1, characterized in that: In step S3, the substrate material is soda-lime glass, FTO or ITO.