TW201137192A - Production method used to produce solar grade silicon - Google Patents

Abstract

The present invention discloses a production method used to produce solar grade silicon, which includes following steps: selecting metallurgical silicon metal of over 98-99.5% purity, wherein the content of boron element is less than 50 ppm and the content of phosphorus element is less than 100 ppm; extracting the boron and the phosphorus in silicon liquid under high temperature; solidifying said silicon liquid; crushing and grinding; surface eroding; water washing and drying; using high temperature plasma to remove boron; performing a refinery to remove phosphorus, aluminum and calcium under high temperature and vacuum condition; and performing unidirectional solidification and post-treatment. The polysilicon ingot obtained by the present invention has boron of < 0.06 ppm, phosphorus of < 0.01 ppm, total metal content of < 0.01 ppm and electrical resistivity of > 1.0 ohm-cm, and can be directly sliced to be used in manufacturing solar battery slice that has photo-electric conversion efficiency of great than 15%. After direct-pulling single crystal, the silicon single crystal can be sliced to manufacture solar battery slice that has photo-electric conversion efficiency of greater than 16%. Additionally, after using zone melting method to pull the single crystal, the silicon single crystal can be sliced to manufacture solar battery slice that has photo-electric conversion efficiency of greater than 17%.

Description

201137192 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] [0001] The present invention relates to a production method for manufacturing a solar grade crucible. [Prior Art] [00〇2] At present, the internationally-used single-crystal manufacturing or polycrystalline foundry solar grade tantalum raw materials, according to the application of the impurity content requirements: Use----------' L Butterfly (Ppm) Fill (ppm) TMI (PPm7^1 straight pull single crystal/zone-------- round one 〇. 06 0. 01 domain fused single crystal polycrystal per spin~-~~~--__ A 0.16 0. 01 〇Τ〇Γ^^ έ Master: Τ Μ I is the total metal content 〇 [0004] The original solar energy 矽 is based on semiconductor grade 矽 (purity

&gt;99. 999999999%) head and tail material, pot bottom material, etc. With the development of the solar cell market, the use of solar energy has increased greatly, and semiconductor secondary materials have been unable to meet the growing demand for the Changeng battery industry. The emergence of the improved Siemens method has alleviated the demand for solar energy to some extent. However, the improved Siemens method still cannot get rid of the high investment, high energy consumption and high pollution of the traditional Siemens method. [0005] In 1975 WACKER took the lead in adopting a physical metallurgy method that was completely different from the Siemens method. After more than 30 years of development in the world, the physical metallurgy method can achieve the metal content &lt; 〇. 011) 1) 1 „ level of cost is also much lower than the improved Siemens method, but the previous invention for phosphorus, boron The control of the element content which is crucial for the solar photovoltaic conversion efficiency decay rate and minority carrier lifetime is limited. Currently, the most reported physical metallurgy method is 100107596. The good phosphorus and boron content is about 〇. The formalities of Form No. A0101, Page 3 of 19, 1002012887-0, 201137192, can only be used in the production of solar cells only after being mixed with modified Siemens or semiconductor secondary materials. [0006] [0007] [0008] [0009] Patent CN1543436A describes a method for plasma deboring, and then using directional solidification to remove metal to produce high purity germanium for solar cells, one of plasma gas source gas, fluorine, hydrogen acid, hydrofluoric acid gas and argon gas. The composition of the mixture gas, the method results in high purity cesium impurities total content of 1 00-250ppm, boron content 〇. 5~2ppm. This method not only has limited purification capacity, but The plasma gas source used is highly toxic and highly corrosive, which is extremely harmful to equipment and operators. Patent CN1 0044441 0C introduces the preparation method of P-type solar grade polycrystalline germanium. The refining part adopts electromagnetic centrifugal technology after blowing oxygen and floating residue. The metal impurities are distributed along the radius, and then the phosphorus is removed by electron bombardment under vacuum, and then directionally solidified to obtain a purity of 99 9999% to 99 99999%, boron bismuth 〇 8 ppm, phosphorus 〇. ippm of high purity 矽 but the method is The lack of effective removal of boron leads to a demanding requirement for the selection of raw materials and equipment for contacting the materials. The harsh conditions of the lanthanum element must be lower than 〇. The practical application is greatly limited. Patent PCT/JP96/02965 The method for the production of a solar-grade polycrystalline silicon, the method of using a vacuum dephosphorization, directional solidification to remove metal impurities, blowing refining to remove carbon and oxygen, and the plasma isolating the oxidized stone. · 6ppm, carbon 10ppm polycrystalline germanium. This method has two directional solidifications, each cut 30% of the waste, that is, at least 51% of the waste is wasted in production. 551 0095 describes a method for the production of high-purity tantalum ingots, 100107596 Form No. A0101 Page 4 / 19 pages 1002012887-0 201137192 Continuous purification of ingots by plasma and zone melting methods, there are several obvious deficiencies in this method: 0010] (1) The raw material grade is required to be high, iron 150 ppm, #吕15 0ppm. [0011] (2) The feed rate is slow (2kg/hr), maintaining two-step melting and one plasma energy consumption is too south. [0012] (3) It is excluded that the impurities are not effectively extracted, so that the continuous impurity content with the production is gradually increased, and the continuous production cannot be performed in a large amount, which is disadvantageous for industrial production. [0013] (4) The boron removal effect is not very satisfactory and can only be reduced to 0.2 ppm. [0014] (5) The photoelectric conversion efficiency of the product made of polycrystalline germanium solar cell is only 13% ° [0015] [Invention] The object of the present invention is to provide a production method for manufacturing solar grade germanium, which can be mass-produced industrially. Environmentally friendly, low-cost, high-quality, high-purity germanium that can be directly used in solar cell production. [0016] In order to achieve the above object, the solution of the present invention is: [0017] A production method for manufacturing a solar grade crucible, which is manufactured according to the following steps: [0018] First step, metallurgical crucible selection: selection of purity in 98~99. More than 5% of metallurgical grade metal stone, butterfly element content &lt;50ppm, filling element content &lt;1 00ppm; [0019] The second step, high temperature liquid extraction: the metallurgical crucible is placed in the intermediate frequency furnace, Melting, inputting extractant 1, while introducing gas, extracting boron from mash, inputting 100107596 extractant 2, and simultaneously extracting phosphorus from sputum by gas; Form No. A0101 Page 5 / 19 pages 1002012887- 0 201137192 [0020] The third step, sputum solidification: the sputum is fished and then poured out of the solidified ingot; [0022] [0024] [0025] [0026] "00271 [0028] [0029 The fourth step, crushing and grinding: after cooling the bismuth ingot, it is mechanically broken into a stone slab of diameter &lt;150mm, and then pulverized into 5 mesh to 500 mesh second powder; the fifth step, surface etching: the glutinous powder is put into Into the reaction kettle, add a chemical etchant, stir; the sixth step, washing and drying: The etched powder is washed 2-20 times with deionized water, dried and dried. The seventh step is high temperature plasma removal: the dried sputum powder is placed in a crucible, heated by electric resistance or induction, and melted. The plasma flame is used to strike the surface of the liquid to remove boron; the eighth step is high temperature vacuum refining: the mash is transferred into a vacuum refining furnace for vacuum refining to remove phosphorus, aluminum and calcium; the ninth step, unidirectional solidification: placing the mash in the crucible Medium, and placed in a unidirectional solidification furnace, solidification of the ingot; Step 10, post-treatment: the surface of the enriched surface of the antimony ingot is cut off to obtain a solar grade antimony ingot. Among them, the second step of the extractant 1, extraction The agent 2 is a mixture of two or more of calcium, magnesium, sodium, indium, iron and shixi compound. The order of addition of the extracting agent 1 and the extracting agent 2 in the second step described above is interchangeable. The two-step extractant 1 and extractant 2 are fed at a melt temperature of 1450 to 180 ° C. The extractant can be used in one shot or in multiple batches. The reaction time after each input is 10 ~300 minutes. 100107596 Form No. A0101 No. 6 Page 19 of 192002012887-0 [0030] 201137192 [0031] The gas of the second step above refers to a mixture of one or more of oxygen, nitrogen, water vapor, hydrogen, argon, etc. [0032] 5〜5小时。 [0033] The chemical etching agent of the above fifth step refers to nitric acid, hydrochloric acid, hydrofluoric acid, acetic acid, sulfuric acid, and the time for the three-step sputum solidification is cooled from 1600 ° C to 1 400 ° C. One or more mixtures; or one or more mixtures of sodium hydroxide, hydrazine hydroxide, aqueous ammonia, sodium carbonate, or the like; or two types of materials are etched in multiple steps. [0034] The surface etching of the fifth step described above is carried out at a temperature of 15 to 95 ° C under normal pressure. [0035] The moisture content of the Shishi powder after the drying in the sixth step is &lt; 3 wt%. [0036] The temperature of the molten mash in the seventh step is maintained between 1420 and 1 800 °C. [0037] The above seventh step of melting sputum is in a separate resistance furnace or induction furnace plus

It is obtained by heat-melting and then moving into a plasma furnace, or directly by heating or melting it by induction or electric resistance on a plasma furnace. [0038] The plasma gas source of the seventh step is a mixture of two or more of nitrogen, hydrogen, argon, helium, oxygen, and water vapor. [0039] The plasma gas source of the seventh step above is preferably argon gas + water vapor, wherein the volume percentage of water vapor is 0 to 50%. [0040] The plasma refining time of the seventh step is 5 to 200 minutes. [0041] The plasma refining of the seventh step above is performed by single furnace refining, or by multi-furnace 1002012887-0 100107596 Form No. A0101 Page 7 / Total 19 pages 201137192 [0044] [0044] [0046] [0046] [0049] [0049] The temperature is maintained between 1414 and 2000 ° C in the vacuum refining of the above-mentioned eighth step of continuous refining in series or single furnace multi-plasma grab series. Solid The vacuum furnace of the eighth step above is true 0._0H0T〇rr.疋

The refining time of the vacuum furnace of the above eighth step is 0.5 to 24 hours. The above-mentioned "step vacuum refining uses a single furnace or a multi-furnace series continuous refining. The order of the plasma decontamination in the seventh step and the high-temperature vacuum refining in the eighth step can be reversed. The unidirectional solidification in the above ninth step is from bottom to top. Solidification, solidification speed is 2~40mm/h. After adopting the above scheme, the invention is prepared by purifying solar grade polycrystalline germanium from ordinary metal, and the method uses high-temperature liquid extraction to reduce boron to below 0.5 ppm in the initial stage of refining. Lowering to below 丨ppm makes the industrial material selection more broad-spectrum, using solidification + surface etching instead of directional solidification cutting technology to reduce metal impurities below 1〇〇ρριη, reducing waste of waste, and more in vacuum Phosphorus and plasma boron removal technology unique multi-furnace, multi-plasma grab series technology, so that the boron content is reduced to less than 6ppm, the phosphorus content is reduced to 0. Olppm or less, and finally directional solidification to make 100107596 Form No. A0101 Page 8 / Total 19 pages 1002012887-0 201137192 ΤΜΙ &lt;0. Olppm, obtaining high quality solar grade polysilicon. [0052] [0052] [0058] [0058] [0058] 100107596 The polycrystalline stone ingot obtained by the present invention, shed &lt; ppm. 06ppm, filled &lt; 0. 01 ppm, TMI &lt; 0. 01 ppm, resistivity &gt; 1. 0 Ω · cm. The solar grade polysilicon is directly sliced for solar cell wafers, achieving a photoelectric conversion efficiency of more than 15%; and straight-drawing single crystal chips are used to fabricate solar cells. The photoelectric conversion efficiency of 16% or more can be obtained; after the single-melting method is used to fabricate the solar cell sheet by the regional melting method, the photoelectric conversion efficiency can be obtained by 17% or more. [Embodiment] Embodiment 1 The production method shown in FIG. For the first step, select 200kg of metallurgical crucible, the impurity content is: iron 1819ppm, ig982ppm, #518 6ppm, ^40ppm,, 15ppm. The second step, high temperature liquid extraction: the metallurgical crucible is placed in the induction furnace, 1 600 ° C melt, input extractant 1: calcium, aluminum, lanthanide compound 100kg, while introducing a nitrogen-oxygen mixture gas 15 5 / mi η, reaction. Time 80 μ η, repeat operation, extract the boron in the mash , boron content is reduced to 1. 〇 3ppm; 1 600 ° C molten state Then, the extractant 2 is added: 50 kg of strontium calcium compound, and 15 L/min of nitrogen gas is introduced at the same time, and the reaction time is 60 min, and the scale in the Xixi liquid is extracted, and the content of the filling is reduced to 3.16 ppm. The third step is to coagulate the sputum: After the liquid is removed from the slag, the solidified ingot is poured out at a speed of 2 hours from 1 600 ° C to 1400 ° C. The fourth step, crushing and grinding: after cooling the cast ingot, it is mechanically broken into form number A0101. Page 9/19 pages 1002012887-0 201137192 [0059] [0061] [0063] Diameter &lt; 150mm stone kiln block, and then pulverized into 250 mesh to 500 mesh stone 〇 powder 〇 fifth step, surface etching: put the glutinous powder into the reaction kettle, first add 6% by weight of hydrochloric acid, at 80 The reaction was stirred at ° C for 20 hours, filtered, washed with deionized water, and then a mixture of 4% by mass of sodium hydroxide and 5% by mass of sodium carbonate was added, and the reaction was stirred at 15 ° C. Hour, then add 9% by weight of nitric acid and 13% by mass of hydrofluoric acid mixture, stir the reaction at 25 ° C for 16 hours, surface etching to further remove boron, phosphorus, iron, aluminum and calcium . The sixth step, the water content is reduced to 60. The water content is reduced to 60. The content of the iron is reduced to 0. 54ppm, the iron content is reduced to 60. 6ppm。 The content of the content is reduced to 15. 6ppm. The seventh step, high temperature plasma removal: the dry tantalum powder is placed in a crucible, heated by electric resistance or induction, after melting, the melt temperature is 1 500 ° C, using a single furnace single plasma grab, gas source: hydrogen, argon and 05ppm。 The water vapor was mixed with a plasma flame against the surface of the liquid for 30 minutes, de boron, the boron content was reduced to 0. 05ppm. The eighth step, high-temperature vacuum refining: the mash is transferred into a vacuum refining furnace, three furnaces are connected in series, vacuum refining, one hour per furnace, melt temperature of 1 500 ° C, vacuum degree &lt; 0. 0001 Torr, disc, The content of both Ming and Ma is &lt; 0. Olppm. The ninth step, one-way solidification: the mash is placed in a crucible, and placed in a one-way condensing furnace to solidify the ingot, and the solidification speed is 10 mm/h. Step 10: Post-treatment: The surface of the enriched surface of the cast antimony ingot is cut off, and the ratio of resection is: 1 5% of the height cut off at the end of the solidification direction to obtain the sun 100107596 Form No. A0101 Page 10 / Total 19 Page 1002012887- [0064] [0064] [0068] [0068] [0068] [0070] [0072] 100107596 energy level bismuth ingot 79kg, impurity iron, is, calcium, phosphorus all &lt; · 01 ppm 'boron 0.05 ppm. Example 2 In combination with Figure 1, the production method is as follows: In the first step, 200 kg of metallurgical crucible is selected, and the impurity content is: iron 1819ρριη, aluminum 982ppm, calcium 186ppm, phosphorus 4〇PPm, lake 15ppm ° second step, high temperature liquid extraction : Put the metallurgical crucible into the induction furnace, melt at 1 600 °C, and input the extractant 1: 6 〇kg of mother, aluminum and lanthanide compound, and introduce 15N/min of nitrogen-oxygen mixture at the same time, the reaction time is 6〇min, repeat Three operations, extracting boron from the mash, the content is reduced to 1.3 ppm; 1600 ° C molten state, and then input the extractant 2: 25 kg of strontium calcium compound, while introducing nitrogen gas 15 L / min, reaction time 6 〇 min, repeat In the second operation, the phosphorus in the mash is extracted, and the phosphorus content is reduced to 2. 〇5j&gt; pra.

The third step is to sputum solidification: the sputum liquid is more than the solidified ingot, the speed is; from 1 600 ° C to 140 01, 2 hours V, the fourth step, crushing and grinding: the cast ingot After cooling, the machine is first broken into a diameter of &lt;150mm, and then pulverized into 250 mesh to 5 mesh. The fifth step is to etch the surface: the powder is put into the reactor and the mass concentration is first added. The reaction was stirred for 1.5 hours, and the reaction was stirred for 1.5 hours. After stirring, the reaction was stirred for 1.5 hours, and the mixture was stirred for 1.5 hours. Wash with water, then add nitric acid with a concentration of 3% by volume and a concentration of 8% by weight of the fluorine-containing form bat No. A0101 Page 11 / 19 pages 1002012887-0 201137192 Acid mixture, stir at 25 ° C The reaction was carried out for 20 hours, filtered, washed with deionized water, finally added with a concentration of 6% by weight of nitric acid, and the reaction was stirred at 80 ° C for 20 hours, and the surface was digested to further remove the collar, fill, iron, Ming and #5. [0075] [0079] [0079] [0079] The sixth step, water washing and drying: the etched powder, washed with deionized water 10 times, dehydrated, dried and dried 5ppm。 The content of the feed is reduced to 8. 5ppm. The content of the feed is reduced to 8.5ppm. The seventh step, high-temperature plasma removal: the dry tantalum powder is placed in the crucible, heated by induction, melted, the melt temperature is 1500 ° C, using a single furnace single plasma grab, gas source: argon and water vapor mixed, with The plasma is reduced to 0.06 ppm. The eighth step, high temperature vacuum refining: the mash is transferred into a vacuum refining furnace, a single furnace, vacuum refining, 2 hours, melt temperature 1 500 ° C, vacuum degree &lt; 0. OOOl Torr, deconstruction, Ming and 4 bow , Fill, Ming and #5 content are all &lt; 0. 01 ppm. The ninth step, one-way solidification: the mash is placed in a crucible, and placed in a one-way condensing furnace to solidify the ingot, and the solidification speed is 10 mm/h. The tenth step, post-treatment: the surface of the enriched surface of the cast antimony ingot is cut off, and the ratio of resection is: 1 5% of the height cut off at the end of the solidification direction, and 77 kg of solar grade Shi Xi key is obtained, and the impurities are iron, good, and filled. &lt;0· Olppm, shed 0. 06ppm 〇Example 3 As shown in Fig. 1, the production method is: 100107596 Form No. A0101 Page 12/19 pages 1002012887-0 201137192 [0080] [0081] [0082] Ο [ 0083] [0084] In the first step, metallurgical stone 〇〇 2〇〇kg was selected, and the impurity content was: iron 1819PPH1, aluminum 982Ppm, calcium l86ppm, phosphorus 4〇m, boron 15pm. The second step is high-temperature liquid extraction: the metallurgical crucible is placed in the induction furnace, 1600 ° C is melted, and the extracting agent n-bow, town, and Shixia compound 140 kg are introduced, and the nitrogen-niobium mixture gas is introduced at 15 L/min. After 60 min, the boron in the mash was extracted, the boron content was reduced to 丨.23 ppm; the molten state was 1600 °C, and then the extractant 2 was added: 25 kg of strontium calcium compound, and 15 L/min of nitrogen gas was introduced, and the reaction time was 6 〇 min. The operation was repeated twice, and the phosphorus in the mash was extracted, and the phosphorus content was lowered to 2 32 ppra. In the third step, the sputum solidifies: the sputum is degreased and then poured out to solidify. The speed is: from 1 600 ° C to 140 ° ° C for 2 hours. The fourth step, crushing and grinding: after cooling the cast ingot, it is mechanically broken into pieces of diameter &lt;150 mm, and then ground into 250 mesh to 5 mesh. [0085] 第五 Step 5, surface Etching: Put the tantalum powder into the reactor, first add hydrochloric acid with a mass concentration of 9%, react at 8 (TC stir) for 14 hours, filter, wash with deionized water, and then add mass percent concentration. 4% potassium hydroxide, stirred at 15 ° C for 40 minutes, filtered, washed with deionized water, then added 4% by mass of acetic acid, mass percent of nitric acid and mass percent concentration of 12 The % hydrofluoric acid mixture is reacted at 25 ° C for 14 hours, and the surface is etched to further remove boron, phosphorus, iron, and the mixture. Step 6: Washing and drying: the etched powder is deionized water. After washing 10 times, after dehydration, drying and drying, the boron content is reduced to 〇. 73Ppm, the scaly content is reduced to 0.85ppm, the iron content is reduced to 76. 2ppm, and the aluminum content is reduced to 100107596. Form No. A0101 Page 3 of 19 Page 1002012887-0 [0086] [0086] [0089] [0090] 3. 8ppm, J The content is reduced to 13. 9ppm. The seventh step, high-temperature plasma removal: the dry tantalum powder is placed in the crucible, heated by induction, after melting, the melt temperature is 1 500 ° C, using a single furnace single plasma grab, gas source: Nitrogen, argon and water vapor are mixed, and the surface of the liquid is blown with a plasma flame for 20 minutes to remove boron, and the boron content is lowered to 0.05 ppm. The eighth step is high-temperature vacuum refining: the mash is transferred into a vacuum refining furnace, and the single furnace is carried out. Vacuum, refining, 2 hours, melt temperature 1 500 ° C, vacuum degree &lt; 0. OOOl Torr, deconstruction, Ming and Ma, 4 bow, Ming content are &lt; 0. Olppm, filling content 0. 01 ppm. Step, one-way solidification: the mash is placed in a crucible, and placed in a unidirectional solidification furnace to solidify the ingot, and the solidification speed is 10 mm/h. Step 10: Post-treatment: enriching the impurities of the cast antimony ingot Surface resection, resection ratio: 15% of the height cut off at the end of the solidification direction, obtain solar energy grade spur 81 kg, impurity iron, transfer average &lt; 0.01 ppm, structure 0 · 01 ppm, paste 0.05 ppm. [0091] BRIEF DESCRIPTION OF THE DRAWINGS [First Embodiment] The first figure is a flowchart of the method of the present invention. DESCRIPTION benefits 100 107 596 Form Number A0101 Page 14 / Total 19 1002012887-0

Claims (1)

201137192 VII. Patent application scope: 1. A production method for manufacturing solar grade crucible, which is characterized in that it is manufactured according to the following steps: First step, metallurgical crucible selection: metallurgy with a purity of 98 to 99. 5 or more is selected. Grade metal bismuth, boron content less than 50 parts per million (50ppm), phosphorus content less than 100 parts per million (lOOppm); second step, high temperature liquid extraction: the metallurgical cesium is placed in the intermediate frequency furnace, Melting, inputting extractant 1, simultaneously introducing gas, extracting boron in sputum, feeding to extractant 2, and simultaneously introducing gas into the filling of Shixi liquid; 〇 third step, sputum solidification: sputum removal After the slag is poured out of the solidified ingot; the fourth step, crushing and grinding: after cooling the bismuth ingot, the machine is first broken into pieces of less than 150 mm in diameter, and then pulverized into 5 to 500 mesh 矽 powder; Etching: Put the tantalum powder into the reaction kettle, add chemical immersion #agent, and mix; 6th step, wash and dry: wash the etched powder with deionized water for 2 to 20 times, dehydrate, dry and dry Seventh step, high temperature, etc. Sub-depletion: Place the dry tantalum powder in a crucible, heat it with resistance or induction, melt it, and use a plasma flame to strike the surface of the liquid to remove boron. Step 8: High-temperature vacuum refining: Move the liquid into a vacuum refining furnace for vacuum Refining dephosphorization, aluminum and about; ninth step, unidirectional solidification: placing the mash in a crucible and placing it in a unidirectional solidification furnace to solidify the ingot; Step 10, post treatment: enriching the impurities of the antimony ingot The surface is cut off to obtain a solar grade bismuth ingot. 2. Production for the manufacture of solar grade crucibles as described in claim 1 of the patent scope 100107596 Form No. A0101 Page 15 of 19 〇〇2012887-〇201137192 Method, in which the second step of extractant 1, extraction The agent 2 is a mixture of two or more kinds of compounds of about, magnesium, sodium, remainder, iron and bismuth. The production method for producing a solar grade crucible according to the first aspect of the patent application, wherein the order of addition of the extractant 1 and the extractant 2 in the second step is interchanged. • The production method for producing solar grade crucible as described in claim 1 wherein the second step of extractant 1 and extractant 2 are fed at a melt temperature of from 1450 degrees Celsius to 18 degrees Celsius. The extractant is put in one time or in multiple batches, and the reaction time after each input is 丨〇 minute to 3 minutes. A method for producing a solar grade crucible according to the first aspect of the invention, wherein the gas of the second step is a mixture of one or more of oxygen, nitrogen, water vapor, hydrogen and argon. • The production method for manufacturing solar grade crucibles as described in claim 1 wherein the third step of solidification of the crucible is cooled from 16 degrees Celsius to 1400 degrees Celsius for 5 hours to 5 hours; hour. The production method for manufacturing a solar grade crucible according to claim 1, wherein the chemical etching agent in the fifth step refers to one or a mixture of nitric acid, hydrochloric acid, hydrofluoric acid, acetic acid and sulfuric acid; or It refers to one or more mixtures of sodium hydroxide, potassium hydroxide, ammonia water and sodium carbonate; or two types of substances are etched in multiple steps. The production method for manufacturing a solar grade stone as described in claim 1, wherein the surface etching in the fifth step is performed at a temperature of 5 degrees Celsius to 95 degrees Celsius. 100107596 The production method for manufacturing solar grade crucible according to claim 1, wherein the weight percentage of the moisture content of the tantalum powder after the sixth step is small 1002012887-0 Form No. A0101 Page 16 of 19 201137192 at 3 percent. 10. The production method for producing a solar grade crucible according to claim 1, wherein the temperature of the seventh step of the molten crucible is maintained between 1420 degrees Celsius and 1800 degrees Celsius. 11. The production method for manufacturing a solar grade crucible according to claim 1, wherein the seventh step of melting the crucible is obtained by moving into a plasma furnace after heating and melting in a separate electric resistance furnace or induction furnace, or directly in the plasma. The sense of use on the furnace should be obtained by direct heating and melting of the resistor. 12. Production for the manufacture of solar grade crucibles as described in claim 1 The method, wherein the plasma gas source of the seventh step uses a mixture of two or more of nitrogen, hydrogen, argon, helium, oxygen and water vapor. 13. The production method for producing a solar grade crucible according to claim 1, wherein the plasma gas source of the seventh step is preferably argon gas plus water vapor, wherein the volume percentage of water vapor is 0 to 50. 14. The method for producing a solar grade crucible according to claim 1, wherein the seventh step of the plasma refining time is from 10 minutes to 200 minutes. 15 as described in claim 1 In the production method of solar grade crucible, the seventh step of plasma refining uses single furnace refining, or continuous refining by multi-furnace series or single furnace multi-plasma grab series. 16. The production method for producing a solar grade crucible according to claim 1, wherein the temperature of the vacuum refining crucible of the eighth step is maintained between 1414 degrees Celsius and 2,000 degrees Celsius. 17. The production method for manufacturing a solar grade crucible according to claim 1, wherein the vacuum refining of the eighth step is obtained by solidifying the ingot after the seventh step of the infusion, or remelting, or It is to move the sputum of the seventh step directly into the true 100107596 Form No. A0101 Page 17 / Total 19 pages 1002012887-0 201137192 18 . 19 . 20 · 21 · 22 Empty refining furnace obtained. The production method for manufacturing a solar grade stone as described in claim 1 of the invention is as follows. The vacuum degree of the vacuum furnace of the eighth step is the shoulder to the ear. The production method for manufacturing a solar grade as described in the scope of claim 4, wherein the refining time of the vacuum furnace of the eighth step is 〇·5 hours to 24 hours. The production process for manufacturing solar energy as described in claim 1 of the patent scope is as follows. The vacuum refining of the eighth step is continuous refining in a single furnace or a multi-furnace. For example, in the production of solar grade crucibles described in claim 1, the plasma decontamination of the seventh step and the high temperature vacuum refining of the eighth step are reversed. For example, in the production of the solar grade crucible described in the first paragraph of the patent scope, the unidirectional solidification of the ninth step is solidification from bottom to top, and the solidification speed is 2 mm per hour to 4 mm per hour. . 100107596 Table·Single bat number A0101 Page 18 of 19 1002012887-0