CN110629241A - Silicon material manufacturing method - Google Patents
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- CN110629241A CN110629241A CN201910871221.9A CN201910871221A CN110629241A CN 110629241 A CN110629241 A CN 110629241A CN 201910871221 A CN201910871221 A CN 201910871221A CN 110629241 A CN110629241 A CN 110629241A
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Abstract
The invention discloses a method for continuously preparing high-purity silicon directly from silicon dioxide or calcium silicate. Silicon dioxide is used as a raw material, calcium oxide is added to assist in melting to form silicate ions, or calcium silicate is directly used as a raw material, and the high-purity silicon is prepared in calcium chloride molten salt through direct electrodeposition. The invention adopts a high-purity quartz crucible as a reaction vessel, a high-purity graphite rod/graphite flake or metal or alloy as an electrode and high-purity argon as protective atmosphere, purifies the calcium chloride fused salt by an intermittent pre-electrolysis technology, and periodically adds a high-purity silicon dioxide or calcium silicate raw material, thereby realizing the continuous preparation of high-purity silicon (> 99.99%) materials by direct electrodeposition. Under the condition of constant current or pulse current, controllable preparation of high-purity crystalline silicon film (> 99.999%), silicon nanowire and crystalline silicon powder can be realized at 850 ℃, and in-situ electro-doping is realized to form p-type/n-type silicon. The invention enables the direct preparation of high purity silicon films from inexpensive silica or calcium silicate for photovoltaic applications.
Description
Technical Field
The invention relates to the technical field of high-purity silicon preparation processes, in particular to a silicon material manufacturing method.
Background
With the rapid development of science and technology, silicon plays an important role in the fields of energy information and the like. At present, a carbothermic method is a main method for producing crude silicon, but the smelting process involves the problems of high energy consumption and heavy pollution in the production process, and the content of various impurity elements in the product is too high. The preparation process of the high-purity silicon adopts a Siemens method, the production process is long, the requirement on equipment is high, and a large amount of waste gas is generated in the production process, so that the cost for preparing the high-purity silicon by the method is high. Therefore, the method is significant in scientific and practical application by paying attention to environmental problems and energy crisis in the world and realizing low-cost and short-flow preparation of silicon materials, particularly high-purity crystalline silicon.
The research of preparing metal and alloy by using a molten salt electrolysis method is widely carried out, and the method has the characteristics of low cost, environmental friendliness, energy conservation, low requirement on equipment, simplicity in operation and the like. Therefore, the silicon material prepared by the fused salt electrolysis method has great advantages. At present, the use of SiO has been studied2The silicon is prepared by electro-deposition in a fluoride system for raw materials, however, the problems of low deposition rate and strong fluoride corrosiveness exist, and the purity of the prepared silicon film is low, so that the requirement of high-purity silicon, such as solar-grade silicon, cannot be met.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the technical problem to be solved by the present invention is to utilize SiO2The deposition rate is increased for the raw material, and the high-purity silicon is manufactured at lower cost.
In order to achieve the purpose, the invention provides a silicon material manufacturing method, which comprises the following steps:
s1, adding CaCl2-(2～5％)SiO2- (2-5%) CaO or CaCl2-(1～5％)CaSiO3Adding raw materials into a quartz crucible; performing vacuum drying intervention treatment at 400-600 ℃ for 24-48 h, and then preserving heat at 850 ℃ under high-purity argon for 24-48 h;
s2, using two high-purity carbon rod electrodes with the same specification as a cathode and an anode respectively, and carrying out intermittent pre-electrolysis for 12-72 h under the voltage of 1.5-2.5V, thereby obtaining a molten salt electrolytic cell system;
s3, slowly inserting the high-purity carbon rod electrode into the molten salt electrolytic cell system; then, preparing high-purity silicon material by adopting constant current and constant voltage continuous electrodeposition; the protective atmosphere is high-purity argon, and the high-purity graphite flake is taken as a matrix for electrodeposition; periodically adding 1-5% of SiO2Or CaSiO3Forming an electrodeposition system;
and S4, washing the cathode product obtained by the electrodeposition with deionized water to remove residual molten salt, and drying to obtain the high-purity silicon material.
Furthermore, the method adopts cheap calcium oxide, silicon dioxide, boron trioxide, antimony trioxide and calcium silicate as raw materials.
Further, the step S2 includes pre-electrolyzing and purifying the molten salt electrolytic cell system, wherein the purifying technical conditions include that two high-purity carbon rods with the same specification are used as a cathode and an anode, pre-electrolyzing is carried out for 4-12 hours at 850 ℃ and 1.5-2.5V, then the electrodes are taken out, the molten salt system is kept warm and stands for 8-12 hours, and the pre-electrolyzing step is repeated for 1-8 times by adopting a new graphite electrode.
Further, the proper amount of B can be added into the molten salt periodically2O3As a doping element, the direct in-situ electro-doping preparation of the p-type silicon film in the electro-deposition process is realized.
Further, Sb may be added periodically into the molten salt in proper amount2O3As a doping element, the direct in-situ electro-doping preparation of the n-type silicon film in the electro-deposition process is realized.
Further, the periodic addition of SiO2Or CaSiO3The calcium chloride can be added into the electrolytic cell periodically after the silicon raw material is consumed, and the time is 48-72 hours.
Further, the periodic addition of SiO2Or CaSiO3And then, standing for 24-48 h.
Further, the substrate for electrodeposition is a high-purity carbon rod or a carbon sheet or a metal and an alloy, and the protection device is a high-purity quartz tube.
Further, the electrodeposition conditions are as follows: constant current of 10-20mA/cm2Or carrying out electrodeposition under the condition of pulse current; the pulse current condition is that the deposition current is 10-20mA/cm for 20-120s2(ii) a Then the current is 0mA/cm for 10-30s2。
Further, the high-purity silicon material prepared by the electrodeposition comprises a solar-grade high-purity silicon film, silicon micro-nano wires and crystal silicon powder.
The invention utilizes calcium oxide to assist in melting silicon dioxide to improve the solubility of the silicon dioxide in calcium chloride, and realizes the continuous preparation of high-purity silicon (> 99.99%) materials (solar-grade crystalline silicon films, silicon micro-nanowires and crystalline silicon powders) directly from cheap silicon dioxide/calcium silicate raw materials by controlling the parameters of electrodeposition and the periodic supplement of silicon raw materials. In addition, the p-type/n-type silicon film can be directly obtained by introducing doping elements to realize in-situ electric doping in the electrodeposition process. The method has the characteristics of low cost, simple operation, short process flow, accurate and controllable product appearance and the like.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a schematic short-flow diagram of a preferred embodiment of the present invention for preparing high-purity silicon material based on electrodeposition;
FIG. 2 is a schematic view showing the construction of an electrolytic cell for producing high purity silicon according to a preferred embodiment of the present invention;
FIG. 3 is a microstructure of a crystalline silicon film prepared by a preferred embodiment of the present invention;
FIG. 4 is a spectrum of a surface-scan energy spectrum of a crystalline silicon film prepared by a preferred embodiment of the present invention;
FIG. 5 is a graph of spectral analysis of a crystalline silicon film prepared in accordance with a preferred embodiment of the present invention;
FIG. 6 is a micro-topography of a cross-section of a crystalline silicon film prepared by a preferred embodiment of the present invention;
FIG. 7 is a diagram of a three-dimensional atom probe analysis of a crystalline silicon film prepared in accordance with a preferred embodiment of the present invention;
FIG. 8 illustrates the elemental content of a crystalline silicon film prepared in accordance with a preferred embodiment of the present invention;
FIG. 9 is a microstructure of a p-type crystalline silicon film prepared by a preferred embodiment of the present invention;
FIG. 10 is a micro-topography of a cross-section of a p-type crystalline silicon film prepared by a preferred embodiment of the present invention;
FIG. 11 is a photocurrent response curve of a p-type crystalline silicon film prepared in accordance with a preferred embodiment of the present invention;
FIG. 12 is a photocurrent response curve of an n-type crystalline silicon film prepared according to a preferred embodiment of the present invention;
FIG. 13 is a typical cyclic voltammogram for silicon micro-nanowires prepared according to a preferred embodiment of the present invention;
FIG. 14 is an X-ray diffraction pattern of silicon micro-nanowires prepared according to a preferred embodiment of the present invention;
FIG. 15 is a photograph of a macro-product of silicon micro-nanowires continuously prepared in the same electrolytic cell according to a preferred embodiment of the present invention;
FIG. 16 is a 1000-fold microscopic topography of a silicon micro-nanowire produced according to a preferred embodiment of the present invention;
FIG. 17 is a 50000 times micro-topography of a silicon micro-nanowire prepared according to a preferred embodiment of the present invention;
FIG. 18 is a microstructure of a silicon wafer prepared according to a preferred embodiment of the present invention;
FIG. 19 is a graph of a surface scan energy spectrum of a silicon wafer prepared according to a preferred embodiment of the present invention;
FIG. 20 is a graph of an energy spectrum analysis of a silicon powder prepared according to a preferred embodiment of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly understood and appreciated by referring to the drawings attached to the specification; the present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
In the drawings, structurally identical elements are represented by like reference numerals, and structurally or functionally similar elements are represented by like reference numerals throughout; the size and thickness of each component shown in the drawings are arbitrarily illustrated, and the present invention is not limited to the size and thickness of each component; the thickness of the components may be exaggerated where appropriate in the figures to improve clarity.
The first preferred embodiment of the present invention: 100g of CaCl2-2.2g SiO22.0g CaO into high purity (C:)>99.99%) in a quartz crucible, and is kept at 500 ℃ for 48h under vacuum, and then the temperature is raised to 850 ℃ for 48h under the protection of high-purity argon. Two high-purity carbon rods with the same specification (>99.999%) as cathode and anode respectively at a voltage of 2.5V for 12h, followed by standing for 12h, and repeating this pre-electrolysis step 4 times to sufficiently remove impurities that may be present in the molten salt. Then, a high-purity graphite carbon sheet with the specification of 60mm multiplied by 6mm multiplied by 1mm and a carbon rod with the diameter of 6mm are respectively used as a cathode and an anode for electrodeposition. The reaction mechanism and flow chart of the present example are shown in FIG. 1, and the structure of the electrolytic cell is shown in FIG. 2. In this case, the electrodeposition was carried out using a pulsed current with a main parameter of 15mA/cm2Electrodepositing for 120s at 0mA/cm2Standing for 20s, and repeating the pulse electrodeposition for 4 h. The surface topography of the final electrodeposition product is shown in fig. 3, and it can be found that the crystalline silicon film prepared by electrodeposition has a compact and uniform structure, and the size of the silicon crystal grains can reach 10 μm. The energy spectrum analysis corresponding to this is shown in fig. 4 and 5, indicating a uniform distribution of silicon element. In addition, FIG. 6 is a cross-sectional view of the crystalline silicon film, and it can be seen that the prepared crystalline silicon film is dense and has a thickness of 20-30 μm. As a result of three-dimensional atom probe analysis of the crystalline silicon film, as shown in FIG. 7, no other elements except silicon were present in the space of 85nm × 82nm × 626 nm. FIG. 8 is a graph showing the impurity element content of the silicon film produced, wherein Ca and Cl are introduced by the calcium chloride molten salt system, and the content of all other impurities including Ti, Mn, Zr, Al, Cu, P, Fe, Ni, Cr, B, Mg, Na, V, K, Co, Zn, Nb, Mo, W, Sb and Sn is far less than 1ppm, which fully demonstrates that the silicon film produced by the present inventionThe prepared silicon material (crystalline silicon film) is high-purity crystalline silicon (99.999%).
The second preferred embodiment of the present invention: 75g of CaCl2-1.6g CaO-1.8g SiO2Adding high purity (>99.99%) in a quartz crucible, the temperature is maintained for 48h at 600 ℃ in vacuum, and then the temperature is raised to 850 ℃ under high-purity argon for 48 h. Two high purity carbon rods (99.999%) with a diameter of 6mm as a cathode and an anode were pre-electrolyzed at a voltage of 2.5V for 14h, followed by standing for 14h, and this pre-electrolysis step was repeated 5 times to sufficiently remove impurities that may be present in the molten salt. Then, a 60mm × 6mm × 1mm graphite carbon sheet and a 6mm diameter carbon rod were used as a cathode and an anode, respectively, to prepare a doped crystalline silicon film by electrodeposition. In this case, doping with B2O3For doping element source, trace amount of B2O3Adding into an electrolytic cell, and then depositing a B element doped p-type silicon film. The deposition conditions were: at 15mA/cm2The electrodeposition was continued for 10 hours under the conditions. The surface microstructure of the silicon film product is shown in fig. 9, and the prepared silicon film surface is compact and uniform crystalline silicon. FIG. 10 is a cross-sectional micro-topography of the product, which is a sufficient demonstration of the dense, uniform silicon film produced by the present invention. FIG. 11 shows a concentration of 100mW/cm for a B-doped p-type crystalline silicon film prepared by electrodeposition2Photocurrent response diagram under illumination. Compared with the current commercial p-type silicon wafer, the p-type silicon wafer can achieve 50-60% of photocurrent response characteristic, and proves that the p-type silicon prepared by the invention has excellent photoelectric property and potential to be directly used for photovoltaic application!
The third preferred embodiment of the present invention: the embodiment of this case is the same as the example, and Sb is used for doping2O3Trace Sb is used as doping element source2O3Adding the solution into an electrolytic cell, and then depositing an Sb element doped n-type silicon film. FIG. 12 shows Sb-doped n-type crystalline silicon film prepared by electrodeposition at 100mW/cm2Photocurrent response diagram under illumination. Compared with the current commercial n-type silicon wafer, the photocurrent response characteristic of 30-40% of the silicon wafer can be achieved, the n-type silicon film prepared by the invention is proved to have excellent photoelectric property, and the short-flow and efficient preparation of the p-type silicon and the n-type silicon films can be realized by regulating and controlling the doping elements!
The fourth preferred embodiment of the present invention: 100g of CaCl2-1.8g CaO-1.4g SiO2Adding high-purity quartz (>99.99%) in a crucible, and keeping the temperature of 400 ℃ for 24h under the vacuum condition. Then the temperature is raised to 850 ℃, high-purity argon is used as protective gas, the temperature is kept for 48 hours, and then two identical high-purity carbon rods (C) with the diameter of 6mm are used>99.999%) as cathode and anode, respectively, and pre-electrolyzing at 2.0V for 8h to remove impurities possibly remained in the molten salt. Then, a high-purity carbon rod with the same specification is used as a cathode substrate, an anode and a reference electrode for deposition, and the whole electrode works under the protection of a high-purity quartz tube. At a constant current density of 10mA/cm2And carrying out electrodeposition for 4 hours under the condition, slowly taking out the cathode, and then replacing a brand new cathode for continuing electrodeposition. Cyclic voltammetry of the electrodeposition process is shown in fig. 13, XRD of the final product is shown in fig. 14, fig. 15 is a photograph of a silicon micro-nanowire product obtained by continuous electrodeposition in the same electrolytic cell, and SEM images of the silicon micro-nanowire product are shown in fig. 16 and fig. 17. From the result of XRD, the electro-deposition product is pure silicon, and the morphology analysis fully proves that the invention can realize the continuous preparation of the silicon micro-nano wire. This indicates that the melting of SiO is assisted by CaO2Electrodeposition is feasible for the continuous production of silicon.
A fifth preferred embodiment of the present invention: adding 120g of CaCl2-2.5gCaSiO3Adding into a high-purity quartz crucible, and keeping the temperature for 30h under the vacuum condition of 450 ℃. Then heating to 850 ℃ in a high-purity argon atmosphere and preserving the heat for 48 hours. Two high-purity (6 mm in diameter) tubes are used>99.999%) are graphite carbon rods as anode and cathode respectively, and the whole electrode is protected by quartz tube. Then the constant current density is 20mA/cm2And performing electrodeposition for 5h under the condition. Fig. 18 is an SEM image of the final product, and the corresponding energy spectrum is shown in fig. 19 and 20. The results show that the calcium silicate can be used for preparing the crystalline silicon powder by electrodeposition.
The foregoing has described in detail preferred embodiments of the present invention; it should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts; therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A silicon material manufacturing method is characterized by comprising the following steps:
s1, adding CaCl2-(2～5％)SiO2- (2-5%) CaO or CaCl2-(1～5％)CaSiO3Adding raw materials into a quartz crucible; performing vacuum drying intervention treatment at 400-600 ℃ for 24-48 h, and then preserving heat at 850 ℃ under high-purity argon for 24-48 h;
s2, using two electrodes as a cathode and an anode respectively, and carrying out intermittent pre-electrolysis for 12-72 h under the voltage of 1.5-2.5V to obtain a molten salt electrolytic cell system;
s3, slowly inserting the electrode into the molten salt electrolytic cell system; the protective atmosphere is high-purity argon, and then constant current and constant voltage continuous electrodeposition is adopted to prepare a high-purity silicon material; periodically adding 1-5% of SiO2Or CaSiO3Forming an electrodeposition system;
and S4, washing the cathode product obtained by the electrodeposition with deionized water to remove residual molten salt, and drying to obtain the high-purity silicon material.
2. The method for preparing high-purity silicon by electrodeposition according to claim 1, wherein the method uses cheap calcium oxide, silicon dioxide, boron trioxide, antimony trioxide and calcium silicate as raw materials.
3. The method for preparing high-purity silicon through electrodeposition according to claim 1 or 2, wherein the step S2 further comprises pre-electrolyzing and purifying the molten salt electrolytic cell system under the condition that two high-purity carbon rods with the same specification are used as a cathode and an anode, pre-electrolyzing for 4-12 hours at 850 ℃ and 1.5-2.5V, taking out the electrodes, keeping the molten salt system at the temperature and standing for 8-12 hours, and repeating the pre-electrolyzing step 1-8 times by using a new graphite electrode.
4. The method for producing high-purity silicon by electrodeposition as claimed in claim 1 or 2, characterized in that an appropriate amount of B can be periodically added to the molten salt2O3As a doping element, the direct in-situ electro-doping preparation of the p-type silicon film in the electro-deposition process is realized.
5. The method for producing high-purity silicon by electrodeposition as claimed in claim 1 or 2, characterized in that an appropriate amount of Sb is periodically added to the molten salt2O3As a doping element, the direct in-situ electro-doping preparation of the n-type silicon film in the electro-deposition process is realized.
6. The method for preparing high-purity silicon by electrodeposition as claimed in claim 1 or 2, wherein the periodic addition of SiO2Or CaSiO3The calcium chloride can be added into the electrolytic cell periodically after the silicon raw material is consumed, and the time is 48-72 hours.
7. The method for preparing high-purity silicon by electrodeposition as claimed in claim 6, wherein the periodic addition of SiO2Or CaSiO3And then, standing for 24-48 h.
8. The method for preparing high-purity silicon by electrodeposition according to claim 1 or 2, wherein the substrate for electrodeposition is a high-purity carbon rod or carbon sheet or metal and alloy, and the protective device is a high-purity quartz tube.
9. The method for preparing high-purity silicon by electrodeposition according to claim 1 or 2, wherein the electrodeposition conditions are: constant current of 10-20mA/cm2Or carrying out electrodeposition under the condition of pulse current; the pulse current condition is that the deposition current is 10-20mA/cm for 20-120s2(ii) a Then the current is 0mA/cm for 10-30s2。
10. The method for preparing high-purity silicon by electrodeposition according to claim 1 or 2, wherein the electrodeposition is used for preparing high-purity silicon material, and the high-purity silicon material comprises solar-grade high-purity silicon film, silicon micro-nano wire and crystalline silicon powder.
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| CN114232033A (en) * | 2021-12-24 | 2022-03-25 | 上海大学 | Method for preparing high-purity iron by high-temperature molten salt electrodeposition |
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