CN101973552A - Method for separating silicon from impurities - Google Patents
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- CN101973552A CN101973552A CN 201010292083 CN201010292083A CN101973552A CN 101973552 A CN101973552 A CN 101973552A CN 201010292083 CN201010292083 CN 201010292083 CN 201010292083 A CN201010292083 A CN 201010292083A CN 101973552 A CN101973552 A CN 101973552A
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Abstract
The invention relates to a method for separating silicon from impurities, belonging to the field of photovoltaics or semiconductors. A silicon material obtained by separation can be used as a raw material of a polycrystalline silicon cast ingot through further purification. The method is characterized by comprising the following steps of: placing the silicon material containing impurities into a container, adding an acid liquid, and controlling temperature, pressure and reaction time; immersing the silicon material in a mixed acid liquid after the reaction is finished, and ultrasonically cleaning the silicon material through an alkali liquid; and finally, ultrasonically cleaning by using pure water to obtain the solar grade silicon material directly used for the polycrystalline silicon cast ingot. According to the method, certain substances difficult to decompose at normal temperature and normal pressure are decomposed by increasing reaction temperature and reaction pressure, such as silicon carbide, silicon nitride, organic adhesives and the like. The impurities can be thoroughly removed by using the method, and the method has the advantages of simple process, low cost and easy industrial popularization.
Description
Technical field
The present invention relates to a kind of of photovoltaic or semiconductor applications silicon and impurity are carried out isolating method, separate the silicon material that obtains can be used as polycrystalline silicon ingot casting through further purification processes raw material.
Background technology
Polycrystalline silicon ingot casting adopts quartz crucible to come splendid attire molten silicon liquid usually, and the main chemical compositions of quartz crucible is a silicon-dioxide.Silicon in the molten state can react with the quartz crucible that directly contacts, and generates silicon monoxide, and silicon monoxide has volatility, can react with the graphite member in the polycrystalline silicon ingot or purifying furnace, produces silicon carbide and carbon monoxide.In addition, the impurity in the quartz crucible also can in simple substance or the form of compound enters silicon melt as iron, aluminium, boron etc., forms new impurity.At present, enter silicon melt, can be used for preventing that the impurity of quartz crucible from entering silicon melt at inner wall of quartz crucible spraying one deck silicon nitride coating usually in order to prevent the impurity in the quartz crucible.Because there are a lot of volatile gaseses on the silicon melt surface, thus a lot of holes can be formed on the silicon ingot surface, and the part silicon nitride can form one with silicon melt through high temperature sintering, so also can contain a lot of silicon nitride impurity in the silicon ingot hole.
After ingot casting is finished, earlier the silicon ingot evolution is become silico briquette, handle, remove the impurity that is deposited on the silicon ingot surface at tail that silico briquette is decaptitated, the silicon material that processing obtains is commonly called as material and flaw-piece material end to end, contains impurity such as more silicon carbide, silicon nitride, aluminum oxide, ferric oxide, boron oxide in these silicon material.These contain the material end to end of impurity and the flaw-piece material can be used as polycrystalline silicon ingot casting once more through purification processes raw material, more currently used impurity-removing methods are earlier with these silicon material process sandblasts, remove most of impurity on surface, and then remove the impurity that silicon material hole the inside is contained by pickling, caustic washing method.The silicon material less for some volumes can't use blasting craft, can only adopt acid corrosion to remove these impurity.Impurity such as some aluminum oxide in the silicon material, ferric oxide, boron oxide are easy to remove by acid corrosion, but be not easy to remove by the method for acid corrosion for silicon carbide and silicon nitride impurity, some silicon carbide, the silicon nitride impurity that especially stick to silicon material hole the inside are not easy to remove especially.Want these Impurity removals, not only the reaction times longer, simultaneously can the more silicon of loss in corrosion process.
Organic gel impurity in the silicon material is mainly derived from the evolution of silicon ingot, because silicon ingot will be fixed on the supporting plate by organic gel earlier before evolution, waits to be installed in after the curing again and carries out evolution in the evolution machine.After evolution was finished, still on some gluing corner that invests silicon ingot, therefore material end to end and the flaw-piece material surface that obtains behind the silicon ingot evolution was stained with many this impurity.
At present, about with silicon and the isolating method of impurity, have relevant report, as: publication number is the drawing method of purification that the Chinese patent of CN101362602A discloses a kind of ingot casting flaw-piece and head material, this method is earlier that pre-treatment is good material, carries out proportioning by resistivity; Shove charge is again found time, heating and melting; Kept high temperature evaporation 2～3 hours down at 1420 ℃～1460 ℃; Seeding draws, and earlier the impurity that swims in liquid level is proposed during drawing, is drawing out polycrystalline silicon rod.After above technology, carry out pickling again, could remove the flaw-piece produced in the ingot casting and head material impurity, thereby ensure the quality of pulled crystal silicon, ensure that its resistance is greater than on 0.5.
Publication number is that the Chinese patent of CN101428252 discloses a kind of sorting method that is mixed with the useless silicon material of impurity, this method is that the useless silicon material that will be mixed with impurity is earlier put in the carbonate solution, the gas that carbonate solution and the reaction of silicon material produce drives remaining silicon material come-up, fish for the silicon material of come-up, realization impurity separates with the silicon material, finishes the sorting of the useless silicon material that is mixed with impurity.Carbonate solution sorting silicon material is adopted in this invention, and efficiency of separation height is applicable to the mass-producing sorting, can replace traditional artificial separation fully.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of with silicon and the isolating method of impurity, adopt this method can decompose some difficult at normal temperatures and pressures materials that decompose, realize that silicon and silicon carbide, silicon nitride etc. are difficult to isolating separate impurities, and in sepn process, reduced the loss of silicon material as far as possible.Table 1 has reacted the situation that has reduced the loss of silicon material of the present invention.
Technical scheme of the present invention is:
A kind of the silicon material that will contain impurity is put into container with silicon and the isolating method of impurity, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning.
A kind of the silicon material that will contain impurity is put into container with silicon and the isolating method of impurity, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning; Temperature is controlled between 30 ℃～340 ℃; Pressure-controlling is between 0.1～10MPa; Reaction times was controlled between 0.1～10 hour.
A kind of the silicon material that will contain impurity is put into container with silicon and the isolating method of impurity, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning; Temperature is controlled between 100 ℃～120 ℃; Pressure-controlling is between 0.2～0.5MPa; Reaction times was controlled between 0.5～10 hour.
A kind of with silicon and the isolating method of impurity, described impurity is any one or several mixing in silicon carbide, silicon nitride, aluminum oxide, ferric oxide, the organic gel.
A kind of with silicon and the isolating method of impurity, described container is high temperature resistant, high pressure resistant, corrosion resistant encloses container.
A kind of with silicon and the isolating method of impurity, described acid solution is any one or several mixing in hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, the phosphoric acid.
A kind of silicon and the isolating method of impurity can be added hydrogen peroxide in the described acid solution, the part by weight that the usage ratio of hydrogen peroxide is pressed the 1-3% of silicon material adds hydrogen peroxide, and the concentration of hydrogen peroxide is 30%.
A kind of with silicon and the isolating method of impurity, described temperature range is controlled between 30 ℃～340 ℃.
A kind of with silicon and the isolating method of impurity, described pressure range is controlled between 0.1～10MPa.
A kind of with silicon and the isolating method of impurity, the described reaction times was controlled between 0.5～10 hour.
A kind of with silicon and the isolating method of impurity, described mix acid liquor is any two kinds or several mixing in hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, acetate, the hydrogen peroxide.
A kind of with silicon and the isolating method of impurity, described alkali lye is any one or two kinds the mixing in sodium hydroxide and the potassium hydroxide.
The implementation result of different technologies scheme of the present invention relatively
Verify repeatedly through the contriver, again in conjunction with above-mentioned implementation result:
Remove silicon carbide impurity, preferred acid solution is: hydrofluoric acid, or nitric acid and hydrofluoric acid, or the mixing acid of sulfuric acid and phosphoric acid also can add hydrogen peroxide.
Remove silicon nitride impurity, preferred acid solution is: hydrofluoric acid, phosphoric acid or nitric acid and hydrofluoric acid, or sulfuric acid and phosphoric acid, or the mixing acid of nitric acid, hydrochloric acid and hydrofluoric acid also can add hydrogen peroxide.
Remove organic gel impurity, preferred acid solution is: nitric acid and hydrogen peroxide, or sulfuric acid and phosphoric acid, or the mixing acid of sulfuric acid, phosphoric acid and hydrogen peroxide.
Principle of work of the present invention and advantage: according to the chemical kinetics theory, the substantial connection of multiple factors such as chemical reaction rate and temperature of reaction, solvent strength, decomposition pressure, reaction times.Adopt the augmenting response temperature, improve decomposition pressure and decompose some difficult materials that decompose under normal temperature, normal pressure, as materials such as silicon carbide, silicon nitride, organic gel.It is more thorough that some silicon carbide, silicon nitride, the organic gel that adopts method provided by the invention silicon material the inside can be contained removed, consumption sour less, and the loss of silicon material is also lower; In addition, this method technology is simple, easy handling.
Embodiment
Embodiment 1, a kind of with silicon and the isolating method of impurity, wherein: the silicon material that will contain impurity is put into container, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning.
Embodiment 2, a kind of with silicon and the isolating method of impurity, wherein: described impurity is silicon carbide, and all the other are with embodiment 1.
Embodiment 3, a kind of with silicon and the isolating method of impurity, wherein: described impurity is silicon nitride, and all the other are with embodiment 1.
Embodiment 4, a kind of with silicon and the isolating method of impurity, wherein: described impurity is aluminum oxide, and all the other are with embodiment 1.
Embodiment 5, a kind of with silicon and the isolating method of impurity, wherein: described impurity is ferric oxide, and all the other are with embodiment 1.
Embodiment 6, a kind of with silicon and the isolating method of impurity, wherein: described impurity is organic gel, and all the other are with embodiment 1.
Embodiment 7, a kind of with silicon and the isolating method of impurity, wherein: described container is high temperature resistant, high pressure resistant, corrosion resistant encloses container, and all the other are with any one embodiment among the embodiment 1-6.
Embodiment 8, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is a hydrofluoric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 9, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is a hydrochloric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 10, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is a nitric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 11, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is a sulfuric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 12, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is a perchloric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 13, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is a phosphoric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 14, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is the mixing acid of nitric acid and hydrofluoric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 15, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is the mixing acid of sulfuric acid and phosphoric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 16, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is the mixing acid of nitric acid, hydrochloric acid and hydrofluoric acid, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 17, a kind of with silicon and the isolating method of impurity, wherein: described acid solution is the mixing acid of sulfuric acid, phosphoric acid and hydrogen peroxide, and all the other are with any one embodiment among the embodiment 1-7.
Embodiment 18, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 30 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 19, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 50 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 20, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 80 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 21, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 120 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 22, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 170 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 23, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 230 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 24, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 300 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 25, a kind of with silicon and the isolating method of impurity, wherein: described temperature is 340 ℃, and all the other are with any one embodiment among the embodiment 1-17.
Embodiment 26, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 0.1MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 27, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 1MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 28, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 2MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 29, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 2MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 30, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 3MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 31, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 4MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 32, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 5MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 33, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 6MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 34, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 7MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 35, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 8MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 36, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 9MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 37, a kind of with silicon and the isolating method of impurity, wherein: described pressure is 10MPa, and all the other are with any one embodiment among the embodiment 1-25.
Embodiment 38, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 0.5 hour, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 39, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 1 hour, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 40, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 2 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 41, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 3 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 42, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 4 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 43, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 5 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 44, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 6 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 45, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 7 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 46, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 8 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 47, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 9 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 48, a kind of with silicon and the isolating method of impurity, wherein: the described reaction times is 10 hours, and all the other are with any one embodiment among the embodiment 1-37.
Embodiment 49, a kind of with silicon and the isolating method of impurity, wherein: described mix acid liquor is: hydrofluoric acid (49%), concentrated nitric acid (68%), the vitriol oil (98%), deionized water, its volume proportion is 2: 1: 1: 4, temperature of reaction is 10 ℃, reaction times is 60min, and all the other are with any one embodiment among the embodiment 1-48.
Embodiment 50, a kind of with silicon and the isolating method of impurity, wherein: described mix acid liquor is: hydrofluoric acid (49%), concentrated nitric acid (68%), the vitriol oil (98%), deionized water, its volume proportion is 2: 1: 1: 4, temperature of reaction is 30 ℃, reaction times is 30min, and all the other are with any one embodiment among the embodiment 1-48.
Embodiment 51, a kind of with silicon and the isolating method of impurity, wherein: described mix acid liquor is hydrofluoric acid (49%), concentrated nitric acid (68%), the vitriol oil (98%), deionized water, its volume proportion is 2: 1: 1: 4, temperature of reaction is 50 ℃, reaction times is 5min, and all the other are with any one embodiment among the embodiment 1-48.
Embodiment 52, a kind of with silicon and the isolating method of impurity, wherein: described alkali lye is sodium hydroxide, potassium hydroxide, deionized water, and its weight proportion is 1: 1: 5, and temperature of reaction is 20 ℃, reaction times is 60min, and all the other are with any one embodiment among the embodiment 1-51.
Embodiment 53, a kind of with silicon and the isolating method of impurity, wherein: described alkali lye is sodium hydroxide, potassium hydroxide, deionized water, and its weight proportion is 1: 1: 5, and temperature of reaction is 40 ℃, reaction times is 30min, and all the other are with any one embodiment among the embodiment 1-51.
Embodiment 54, a kind of with silicon and the isolating method of impurity, wherein: described alkali lye is sodium hydroxide, potassium hydroxide, deionized water, and its weight proportion is 1: 1: 5, and temperature of reaction is 70 ℃, reaction times is 6min, and all the other are with any one embodiment among the embodiment 1-51.
Embodiment 55, a kind of with silicon and the isolating method of impurity, wherein: the silicon material that will contain impurity is put into container, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning;
Temperature is controlled between 30 ℃～340 ℃; Pressure-controlling is between 0.1～10MPa; Reaction times was controlled between 0.1～10 hour.
Embodiment 56, a kind of the silicon material that will contain impurity is put into container with silicon and the isolating method of impurity, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning; Wherein:
Temperature is controlled between 100 ℃～120 ℃; Pressure-controlling is between 0.2～0.5MPa; Reaction times was controlled at 0.5～10 hour.
Embodiment 57, a kind of with silicon and the isolating method of impurity, wherein: temperature is controlled at 30 ℃; Pressure-controlling is at 10MPa; Reaction times was controlled between 6 hours.All the other are with embodiment 55.
Embodiment 58, a kind of with silicon and the isolating method of impurity, wherein: temperature is controlled at 340 ℃; Pressure-controlling is at 0.1MPa; Reaction times was controlled at 10 hours.All the other are with embodiment 55.
Embodiment 59, a kind of with silicon and the isolating method of impurity, wherein: temperature is controlled at 200 ℃; Pressure-controlling is at 3MPa; Reaction times was controlled at 0.1 hour.All the other are with embodiment 55.
Embodiment 60, a kind of with silicon and the isolating method of impurity, wherein: temperature is controlled at 100 ℃; Pressure-controlling is at 0.5MPa; Reaction times was controlled at 0.1 hour.All the other are with embodiment 56.
Embodiment 61, a kind of with silicon and the isolating method of impurity, wherein: temperature is controlled at 120 ℃; Pressure-controlling is at 0.2MPa; Reaction times was controlled at 10 hours.All the other are with embodiment 56.
Embodiment 62, a kind of with silicon and the isolating method of impurity, wherein: temperature is controlled at 110 ℃; Pressure-controlling is at 0.4MPa; Reaction times was controlled at 1 hour.All the other are with embodiment 56.
Embodiment 63, a kind of the silicon material that will contain impurity is put into container with silicon and the isolating method of impurity, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning;
Wherein: temperature is controlled at 110 ℃; Pressure-controlling is at 0.4MPa; Reaction times was controlled at 1 hour; Add hydrogen peroxide in mixing acid, 3% the part by weight that the usage ratio of hydrogen peroxide is pressed the silicon material adds hydrogen peroxide, and the concentration of hydrogen peroxide is 30%.
Embodiment 64,
A kind of with silicon and the isolating method of impurity, wherein: add hydrogen peroxide in acid solution, 1% the part by weight that the usage ratio of hydrogen peroxide is pressed the silicon material adds hydrogen peroxide, and the concentration of hydrogen peroxide is 30%.All the other are with embodiment 61.
Embodiment 65,
A kind of with silicon and the isolating method of impurity, wherein: add hydrogen peroxide in acid solution, 2% the part by weight that the usage ratio of hydrogen peroxide is pressed the silicon material adds hydrogen peroxide, and the concentration of hydrogen peroxide is 30%.All the other are with embodiment 60.
Temperature is controlled between 100 ℃～120 ℃; Pressure-controlling is between 0.2～0.5MPa; Reaction times was controlled at 0.5～10 hour.
The test example:
The test effect contrast is as follows:
Existing conventional solution is as follows: a kind of with silicon and the isolating method of impurity, wherein: the silicon material that will contain impurity is put into container, adds acid solution, handles under normal temperature, normal pressure situation; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning.
Silicon nitride can form one with silicon melt through high temperature sintering, so also can contain a lot of silicon nitride impurity in the silicon ingot hole.But be not easy to remove by the method for acid corrosion for silicon carbide and silicon nitride impurity, some silicon carbide, the silicon nitride impurity that especially stick to silicon material hole the inside are not easy to remove especially.Want these Impurity removals, not only the reaction times longer, simultaneously can the more silicon of loss in corrosion process.
The problem that existing conventional solution exists is that the loss of silicon material is serious: add acid solution, handle under normal temperature, normal pressure situation; Because silicon carbide and silicon nitride impurity and silicon material separation difficulty, silicon carbide and silicon nitride impurity could effectively be removed in the depths that needs acidic substance to be deep into the silicon material, and the silicon material of carrying secretly like this loses about about 10%.
But the employing technical solution of the present invention is handled under the high temperature and high pressure situation; Silicon carbide and silicon nitride impurity separate with the silicon material and become relatively easy, and the silicon material loses about about 4%.
Handle if adopt under hydrogen peroxide and the high temperature and high pressure situation; Silicon carbide separates with the silicon material with silicon nitride impurity and becomes more relatively easy, and the silicon material loses about about 2%.
Thinking routinely: though hydrogen peroxide is helpful to decon, its corrosion dissolution negative effect to the silicon material also still exists.
But the present invention finds to select the hydrogen peroxide consumption of proper ratio, and cooperates follow-up high-temperature high-pressure craft, and the loss of silicon material reduces on the contrary.
Because the silicon material of gained can be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting, it costs an arm and a leg, and the silicon material of saving several percentage points is very significant.
Its content arrangement is tabulated form:
Table 1:
Claims (12)
1. one kind with silicon and the isolating method of impurity, and it is characterized in that: the silicon material that will contain impurity is put into container, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning.
2. one kind with silicon and the isolating method of impurity, and it is characterized in that: the silicon material that will contain impurity is put into container, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning;
Temperature is controlled between 30 ℃～340 ℃; Pressure-controlling is between 0.1～10MPa; Reaction times was controlled between 0.1～10 hour.
3. one kind with silicon and the isolating method of impurity, and it is characterized in that: the silicon material that will contain impurity is put into container, adds acid solution, controlled temperature, pressure and reaction times; After question response is complete, places mix acid liquor to soak in the silicon material again, and, pass through the pure water ultrasonic cleaning at last, promptly obtain to be directly used in the solar energy level silicon material of polycrystalline silicon ingot casting by the alkali lye ultrasonic cleaning;
Temperature is controlled between 100 ℃～120 ℃; Pressure-controlling is between 0.2～0.5MPa; Reaction times was controlled between 0.5～10 hour.
4. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: described impurity is any one or several mixing in silicon carbide, silicon nitride, aluminum oxide, ferric oxide, the organic gel.
5. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: described container is high temperature resistant, high pressure resistant, corrosion resistant encloses container.
6. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: described acid solution is any one or several mixing in hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, the phosphoric acid.
7. as claim 1 or 2 or 3 or 4 or 5 or 6 described a kind of with silicon and the isolating method of impurity, it is characterized in that: can add hydrogen peroxide in the described acid solution, the part by weight that the usage ratio of hydrogen peroxide is pressed the 1-3% of silicon material adds hydrogen peroxide, and the concentration of hydrogen peroxide is 30%.
8. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: described temperature range is controlled between 30 ℃～340 ℃.
9. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: described pressure range is controlled between 0.1～10MPa.
10. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: the described reaction times was controlled between 0.5～10 hour.
11. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: described mix acid liquor is any two kinds or several mixing in hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, acetate, the hydrogen peroxide.
12. as claim 1 or 2 or 3 described a kind of with silicon and the isolating method of impurity, it is characterized in that: described alkali lye is any one or two kinds the mixing in sodium hydroxide and the potassium hydroxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102920838A CN101973552B (en) | 2010-09-21 | 2010-09-21 | Method for separating silicon from impurities |
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| CN2010102920838A CN101973552B (en) | 2010-09-21 | 2010-09-21 | Method for separating silicon from impurities |
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| CN101973552B CN101973552B (en) | 2012-11-14 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502652A (en) * | 2011-11-07 | 2012-06-20 | 江西旭阳雷迪高科技股份有限公司 | Cleaning process for polycrystalline material |
| CN102671885A (en) * | 2012-05-18 | 2012-09-19 | 宁夏隆基硅材料有限公司 | Device and method for removing quartz from monocrystalline silicon pot material |
| CN102757051A (en) * | 2012-04-19 | 2012-10-31 | 镇江环太硅科技有限公司 | Method for performing recovery treatment on waste layer silicon material |
| CN102989723A (en) * | 2012-10-24 | 2013-03-27 | 嘉兴嘉晶电子有限公司 | Method for washing high-resistivity and low-resistivity silicon materials |
| CN103011168A (en) * | 2011-09-23 | 2013-04-03 | 上海普罗新能源有限公司 | Cleaning method of polycrystalline silicon raw material |
| CN103769383A (en) * | 2012-10-23 | 2014-05-07 | 宿迁宇龙光电科技有限公司 | Silicon raw material washing method |
| CN104445206A (en) * | 2014-10-09 | 2015-03-25 | 浙江大学 | Method for cleaning silicon nitride on surface of silicon block |
| CN104637786A (en) * | 2015-01-21 | 2015-05-20 | 江西久顺科技有限公司 | Method for removing silicon nitride coating from IC (Integrated Circuit) sheet stock |
| CN104843711A (en) * | 2015-04-23 | 2015-08-19 | 山西潞安太阳能科技有限责任公司 | Novel solar silicon material pickling method |
| CN106115715A (en) * | 2016-06-26 | 2016-11-16 | 河南盛达光伏科技有限公司 | Polycrystalline silicon ingot casting partly melts the circulation tailing cleaning treatment method that technique produces |
| CN108987677A (en) * | 2018-07-18 | 2018-12-11 | 大连理工大学 | The method that silicon wafer cut by diamond wire waste recovery is used for lithium ion battery negative material preparation |
| CN109950137A (en) * | 2019-04-11 | 2019-06-28 | 江苏美科硅能源有限公司 | One kind is for handling cutting belt adhesive tape fragment material processing method |
| CN110508552A (en) * | 2019-09-27 | 2019-11-29 | 江苏美科硅能源有限公司 | A kind of processing method of the primary silicon material of the attached oxide in surface |
| CN114308814A (en) * | 2021-12-22 | 2022-04-12 | 宁波尤利卡太阳能股份有限公司 | Method for cleaning graphite boat |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639063A (en) * | 2002-02-28 | 2005-07-13 | 佳能株式会社 | Process of producing multicrystalline silicon substrate and solar cell |
| CN101531366A (en) * | 2009-03-09 | 2009-09-16 | 常州有则科技有限公司 | Method for cleaning polycrystalline silicon material |
| US7780938B2 (en) * | 2006-04-13 | 2010-08-24 | Cabot Corporation | Production of silicon through a closed-loop process |
-
2010
- 2010-09-21 CN CN2010102920838A patent/CN101973552B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639063A (en) * | 2002-02-28 | 2005-07-13 | 佳能株式会社 | Process of producing multicrystalline silicon substrate and solar cell |
| US7780938B2 (en) * | 2006-04-13 | 2010-08-24 | Cabot Corporation | Production of silicon through a closed-loop process |
| CN101531366A (en) * | 2009-03-09 | 2009-09-16 | 常州有则科技有限公司 | Method for cleaning polycrystalline silicon material |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011168A (en) * | 2011-09-23 | 2013-04-03 | 上海普罗新能源有限公司 | Cleaning method of polycrystalline silicon raw material |
| CN102502652A (en) * | 2011-11-07 | 2012-06-20 | 江西旭阳雷迪高科技股份有限公司 | Cleaning process for polycrystalline material |
| CN102757051A (en) * | 2012-04-19 | 2012-10-31 | 镇江环太硅科技有限公司 | Method for performing recovery treatment on waste layer silicon material |
| CN102671885A (en) * | 2012-05-18 | 2012-09-19 | 宁夏隆基硅材料有限公司 | Device and method for removing quartz from monocrystalline silicon pot material |
| CN103769383A (en) * | 2012-10-23 | 2014-05-07 | 宿迁宇龙光电科技有限公司 | Silicon raw material washing method |
| CN103769383B (en) * | 2012-10-23 | 2016-05-04 | 宿迁宇龙光电科技有限公司 | A kind of cleaning method of silicon raw material |
| CN102989723A (en) * | 2012-10-24 | 2013-03-27 | 嘉兴嘉晶电子有限公司 | Method for washing high-resistivity and low-resistivity silicon materials |
| CN104445206A (en) * | 2014-10-09 | 2015-03-25 | 浙江大学 | Method for cleaning silicon nitride on surface of silicon block |
| CN104637786B (en) * | 2015-01-21 | 2018-02-27 | 江西久顺科技有限公司 | A kind of method of silicon nitride coating in removal IC sheet stocks |
| CN104637786A (en) * | 2015-01-21 | 2015-05-20 | 江西久顺科技有限公司 | Method for removing silicon nitride coating from IC (Integrated Circuit) sheet stock |
| CN104843711A (en) * | 2015-04-23 | 2015-08-19 | 山西潞安太阳能科技有限责任公司 | Novel solar silicon material pickling method |
| CN106115715A (en) * | 2016-06-26 | 2016-11-16 | 河南盛达光伏科技有限公司 | Polycrystalline silicon ingot casting partly melts the circulation tailing cleaning treatment method that technique produces |
| CN108987677A (en) * | 2018-07-18 | 2018-12-11 | 大连理工大学 | The method that silicon wafer cut by diamond wire waste recovery is used for lithium ion battery negative material preparation |
| CN109950137A (en) * | 2019-04-11 | 2019-06-28 | 江苏美科硅能源有限公司 | One kind is for handling cutting belt adhesive tape fragment material processing method |
| CN110508552A (en) * | 2019-09-27 | 2019-11-29 | 江苏美科硅能源有限公司 | A kind of processing method of the primary silicon material of the attached oxide in surface |
| CN114308814A (en) * | 2021-12-22 | 2022-04-12 | 宁波尤利卡太阳能股份有限公司 | Method for cleaning graphite boat |
| CN114308814B (en) * | 2021-12-22 | 2024-01-12 | 宁波尤利卡太阳能股份有限公司 | Method for cleaning graphite boat |
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