CN105755532A - Crystalline silicon preparation method and crystalline silicon - Google Patents
Crystalline silicon preparation method and crystalline silicon Download PDFInfo
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- CN105755532A CN105755532A CN201610227154.3A CN201610227154A CN105755532A CN 105755532 A CN105755532 A CN 105755532A CN 201610227154 A CN201610227154 A CN 201610227154A CN 105755532 A CN105755532 A CN 105755532A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
Abstract
The invention provides a crystalline silicon preparation method.The crystalline silicon preparation method includes that polycrystalline silicon and a dopant are added into a crucible of a crystalline silicon ingot furnace or a single crystal furnace; in presence of protective gas, the polycrystalline silicon and the dopant are heated to melt completely to form silicon melts, crystalline silicon growth parameters are adjusted to enable the silicon melts to start to grow crystals, and in a crystal growing process, when resistivity of the crystals reaches clinical resistivity, new silicon melts formed by the polycrystalline silicon are replenished into residual silicon melts in the crucible to enable the resistivity of the crystals to be adjusted to target resistivity, and the new silicon melts continue growing crystals so as to obtain crystalline silicon with target yield after crystallization of the silicon melts in the crucible is completed.The crystalline silicon preparation method is capable of solving the problems of too many low-resistivity regions, scattered resistivity distribution and low crystalline silicon yield in the prior art.The invention further provides the crystalline silicon.
Description
Technical field
The present invention relates to solar cell material technical field, particularly relate to preparation method and the crystalline silicon of a kind of crystalline silicon.
Background technology
In all kinds of solaodes of photovoltaic industry, crystalline silicon (monocrystal silicon, polysilicon) solaode occupies extremely important status, at present in occupation of the share of photovoltaic market about more than 75%.Mostly the silicon sheet material producing crystal silicon solar energy battery is to make by polycrystalline silicon ingot casting or by czochralski silicon monocrystal is processed.
For crystal silicon solar energy battery, its photoelectric transformation efficiency is the resistivity with silicon chip is closely-related.Generally, for the preparation of high efficiency solar cell, the resistivity of crystalline silicon material to control the scope at 1～3 Ω cm, and resistivity genesis analysis span is little as much as possible simultaneously.Therefore, in order to meet the requirement of cell piece processing, it is necessary to obtain the electric property of requirement in crystalline silicon growth course by regulating the concentration of adulterant.
Available adulterant has group-III element boron, aluminum, gallium, indium, thallium (preparation P-type silicon sheet) and group Ⅴ element nitrogen, phosphorus, arsenic, antimony, bismuth (preparation N-type silicon chip).Wherein, because boron segregation coefficient (0.8) in silicon is closer to 1, in crystal growing process, segregation is less, silicon crystal resistivity distribution uniform, is routinely incorporated into appropriate boron to obtain the resistivity P-type crystal silicon material for 1-3 Ω cm.But, battery prepared by boron-doping silicon chip there will be light decay phenomenon after using, and reduces the conversion efficiency of battery, currently mainly thinks that doped with boron atom is relevant with the boron-oxygen complex that the oxygen atom in crystalline silicon is formed under sunlight.By can avoid the generation of boron-oxygen complex with gallium, phosphorus replacement boron or boron and gallium co-doped long crystal in next life silicon, it is suppressed that optical attenuation phenomenon.But the segregation coefficient of gallium less (0.008) causes that the electrical resistivity range of crystalline silicon obtained is wider, gallium doping content particularly in the crystalline silicon features head of polycrystalline silicon ingot of directional solidification (afterbody of czochralski silicon monocrystal) finally grown in long brilliant process is higher, resistivity is on the low side, the region (1-3 Ω cm) that resistivity meets requirement is very few, the yield that can be used for preparing the crystalline silicon of efficient solar battery only has 50-60%, and this makes the high cost of growth crystalline silicon；And for the less V race's doped chemical of the segregation coefficients such as phosphorus, there is also prepared crystalline silicon resistivity skewness equally, problem that yield is less.
Existing technology is contra-doping technology (such as CN104532345) in order to what control that resistivity mainly takes, compensation by donor concentration (such as phosphorus), reduce acceptor impurity (such as the gallium) concentration in melt, so that the resistivity of silicon crystal is risen to qualified region, but counter mixing may introduce substantial amounts of contra-doping element, even obtaining a part of transoid silicon materials, the efficiency causing battery is lower.
Thus, need badly a kind of rationally effective approach of exploitation to control the resistivity of crystalline silicon obtaining the high crystalline silicon of resistivity concentration degree, improve crystalline silicon yield, reduce photo attenuation to improve crystal in the utilization rate preparing on efficient solar battery, to reduce battery cost be have very important meaning.
Summary of the invention
In view of this, the preparation method that the invention provides a kind of crystalline silicon, in order to solve the problem that resistivity region on the low side is more, resistivity distribution is not concentrated, crystalline silicon yield is relatively low of the crystalline silicon prepared in prior art.The present invention repeatedly adds polycrystalline silicon material in growing in the polycrystalline silicon material and adulterant passing through fusing in crucible in brilliant process of crystalline silicon, and do not introduce new doped chemical, the progressively concentration of the doped chemical in dilution silicon melt, by doped chemical concentration in control melt thus realizing the doping content of freezing solid, reach the effect of Uniform Doped, so that resistivity distribution tends to be steady more, thus the resistivity qualification rate of crystalline silicon controlling to grow is higher, the crystalline silicon material that resistivity concordance is good, crystal yield is higher, photo attenuation is relatively low.
First aspect, the preparation method that the invention provides a kind of crystalline silicon, comprise the following steps:
Polycrystalline silicon material and adulterant are joined in the crucible of crystalline silicon ingot casting furnace or single crystal growing furnace；Described adulterant is containing one or more in the simple substance of doped chemical, alloy, oxide and nitride, and described doped chemical is boron and gallium, or is the one in boron, gallium and phosphorus；
Under protective gas exists, heating makes described polycrystalline silicon material and adulterant be completely melt to form silicon melt, regulate crystalline silicon growth parameter(s), described silicon melt is made to start to grow crystal, in the process of described growth crystal, when the resistivity of crystal reaches critical resistance rate, remaining silicon melt is added a certain amount of described polycrystalline silicon material in crucible and forms new silicon melt, the resistivity making the crystal grown by new silicon melt is adjusted target resistivity, described new silicon melt continues long crystalline substance, after treating the silicon melt crystallization in crucible, obtain the crystalline silicon of target yield, the target yield of described crystalline silicon is 75～99%；Wherein, in the process of described growth crystal, including adding described polycrystalline silicon material at least one times, described critical resistance rate is 1-3 Ω cm, and described target resistivity is 1-3 Ω cm, and described target resistivity is more than or equal to described critical resistance rate；Described yield refers in target crystal silicon, the accounting of resistivity crystalline silicon between 1-3 Ω cm.
Should be noted that, heretofore described yield refers to the accounting of the crystalline silicon being positioned at the qualified region of the acceptable resistivity of industry (1-3 Ω cm).It is understood that when in the present invention initial time crucible in initial electrical resistivity (being generally equal to target resistivity) corresponding to material be 3 Ω cm, critical resistance rate be 1 Ω cm time, the resistivity separation delta ρ=2 Ω cm that gained yield of the present invention is corresponding；And when the siding-to-siding block length Δ ρ of initial electrical resistivity and critical resistance rate is less than 2 Ω cm, (if initial electrical resistivity is 2.4 Ω cm, critical resistance rate is 1 Ω cm), the electrical resistivity range spacing (Δ ρ=3-1=2 Ω cm) that resistivity spacing that gained yield of the present invention is corresponding (Δ ρ=1.4 < 2 Ω cm) is bound to more corresponding than the qualified region of industry internal resistance rate is little.
Preferably, in described ingot furnace or single crystal growing furnace, it is additionally provided with feed supplementing device, in described feed supplementing device, puts into polycrystalline silicon material to be added.As long as the destination device being capable of adding polycrystalline silicon material in described ingot furnace or single crystal growing furnace all can as feed supplementing device.
In the present invention, the described polycrystalline silicon material in the polycrystalline silicon material that loads in crucible, feed supplementing device is virgin polycrystalline silicon material, purity be 6N and more than.
In the present invention, described in the polycrystalline silicon material added be liquid or solid-state, liquid silicon material or solid silicon material can be added in described feed supplementing device.When adding the second polycrystalline silicon material of solid-state, it is necessary to the thermal field controlled in stove makes the second polycrystalline silicon material of addition be completely melt, after new silicon melt to be formed, then starts the growth of crystalline silicon.When add liquid the second polycrystalline silicon material time, the second polycrystalline silicon material of described liquid can be through adopting other devices to be heated into liquid in advance the second polycrystalline silicon material of solid-state, then again water conservancy diversion in this feed supplementing device.After second polycrystalline silicon material to be added silicon melt phase original in crucible is mixed homogeneously and formed new silicon melt, then start the growth of crystalline silicon.
Preferably, described second polycrystalline silicon material is liquid.So improve the long brilliant efficiency of crystalline silicon, save the time.
Preferably, described crystalline silicon is monocrystal rod or polycrystal silicon ingot.Czochralski silicon monocrystal can be obtained by vertical pulling method, or directional solidification method obtains polycrystal silicon ingot.The regulation and control of the growth parameter(s) of described crystalline silicon, can adopt method of the prior art to carry out.
In the present invention, in the growth course of crystalline silicon, described in silicon melt remaining in crucible, add described polycrystalline silicon material, can carry out 1 time, can also carry out repeatedly, as added 2 times, add 20 times, this Main Basis target resistivity, critical resistance rate and desired target yield and determine, it is preferred to 2-20 time.It is understood that when adding described polycrystalline silicon material each time, formed in crucible new silicon melt start to continue long brilliant time, the resistivity of the harsh crystal block section afterbody of monocrystal silicon (head of polycrystal silicon ingot) grown all reaches target resistivity.
Preferably, when the gross mass of the described polycrystalline silicon material added in described crucible reaches initial in crucible during K times of the quality sum of polycrystalline silicon material and adulterant, stop in described crucible reinforced, after treating the silicon melt crystallization in crucible, obtain crystalline silicon, whereinWherein, Y0For target yield, Y0It is 75%～99%, Y1The yield of gained crystalline silicon when for not adding described polycrystalline silicon material.It is understood that Y0> Y1。
Wherein, for doped chemical containing only gallium, when the mixture in initial crucible not being diluted, carry out long crystalline substance, final Y by the growth parameter(s) of normal lens silicon1It is about 50%-60%.
And for doped chemical containing only P elements, its Y1It is about 70-80%；
And be that gallium, boron are co-doped with for diluent, its Y1It is about 50-90%.
And for doped chemical containing only boron element, its Y1It is about 90%, it is preferable that described target yield Y0For 91%-99%.For the boron element bigger containing independent segregation coefficient, mode preferably by continuous charging is fed in raw material, now target resistivity is with critical resistance rate closely, so can obtain the crystalline silicon of resistivity substantially steadily (close to fixed value), it is possible to be reduced as far as the light decay problem caused because resistivity is relatively uneven.Although the yield of single boron-doping promotes very notable, but the accounting of stable crystalline silicon near target resistivity (such as 2.4 Ω cm) be far above prior art in do not add the situation of silicon material.When selecting continuous charging, it is preferable that make the charging rate of described continuous charging be substantially equal to the speed of growth of crystal.
Preferably, when described adulterant is containing only when having gallium, described K is 0.6-50, it is preferable that K is 0.6-40, it is preferred that becoming K is 1-40.
When described adulterant is containing only when having phosphorus, described K is 0.2-30, it is preferable that K is 1-20.
Contain boron and gallium when described adulterant, described K is 0.6-50.
When described adulterant is containing only when having boron, described K is 0.1-9, it is preferred to 2-5.
In the present invention, for the doped chemical (such as gallium) that segregation coefficient is less, growth along with crystal, in silicon melt, the concentration of doped chemical is gradually increased, resistivity is gradually lowered, when it reaches critical resistance rate, in described crucible, add described polycrystalline silicon material to dilute the concentration of doped chemical, to promote resistivity, make the resistivity of crystal again be recalled to target resistivity；After adding described polycrystalline silicon material, the resistivity of crystal still can continue to reduce along with the growth of crystal, but remains above critical resistance rate, meets the resistivity requirement in silicon chip of solar cell industry；When the resistivity of the crystal of growth reaches critical resistance rate again, described polycrystalline silicon material is added again in crucible, the gross mass of the polycrystalline silicon material added to be transferred to target resistivity, circulates with this, until can make the crystalline silicon finally given reach desired target yield.
Preferably, described adulterant is containing only when having gallium, and described adulterant is gallium, gallium-silicon alloy or gallium nitride, but is not limited to this, if for this area can containing gallium adulterant.
When described adulterant is containing only when having phosphorus, described adulterant is phosphorus pentoxide or phosphorus-silicon alloy, but is not limited to this.
When containing boron and gallium when described adulterant, described adulterant is gallium and the mixture of boron-silicon alloy, or the mixture of gallium-silicon alloy and boron-silicon alloy, or the mixture of gallium and boron powder, or the mixture of gallium-silicon alloy and boron powder, but it is not limited to this.
Preferably, when described adulterant is containing only when having boron, described adulterant is boron-silicon alloy, boron nitride or boron powder, but is not limited to this.
Preferably, when described adulterant is containing only when having gallium, in the silicon melt that the mixture melt of described polycrystalline silicon material and adulterant is formed, the content of gallium element is 5.7E+17～1.82E+18atoms/cm3.Namely gallium element atomic volume concentration in the described polycrystalline silicon material in crucible when initial is 5.7E+17～1.82E+18atoms/cm3.The ratio of the foreign atom of described gallium adulterant and the silicon raw material atomic number of described polycrystalline silicon material is 11.3-36.3ppma.The resistivity that so can make the part afterbody of polycrystal silicon ingot (head of monocrystal silicon) of the crystalline silicon grown at first reaches initial electrical resistivity (being generally equal to purpose resistivity, such as 1-3 Ω cm).The content of gallium element in the mixture of described polycrystalline silicon material and adulterant, it is possible to relation between material in crucible when setting initial according to required initial electrical resistivity.Similarly, in the new silicon melt formed after adding described polycrystalline silicon material in described crucible, in continuing long brilliant process, gallium concentration in silicon melt remains at 5.7E+17 to 1.82E+18atoms/cm3Between.
In the present invention, in crucible, described polycrystalline silicon material and adulterant are completely melt that in the silicon melt formed, the content of described doped chemical can determine according to the initial electrical resistivity (afterbody of polycrystal silicon ingot or the head of silicon single crystal rod) of the required crystalline silicon grown at first.Described initial electrical resistivity is 1-3 Ω cm, it is preferred to 1.5-3 Ω cm, more preferably 2-3 Ω cm.It should be noted that described initial electrical resistivity can more than or equal to described target resistivity.Preferably, described initial electrical resistivity is equal to described target resistivity.
Preferably, when described adulterant is containing only when having phosphorus, in the silicon melt that the mixture melt of described polycrystalline silicon material and adulterant is formed, the content of P elements is 4.37E+15～1.39E+16atoms/cm3.Namely P elements atomic volume concentration in the described polycrystalline silicon material in crucible when initial is 4.37E+15～1.39E+16atoms/cm3.The resistivity that so can make the part of the crystalline silicon grown at first reaches initial electrical resistivity (being generally equal to purpose resistivity, such as 1-3 Ω cm).
Preferably, when described adulterant is containing only when having boron, boron element atomic volume concentration in the described polycrystalline silicon material in crucible when initial is 5.7E+15～1.82E+16atoms/cm3。
When containing boron and gallium when described adulterant, can arbitrarily regulate and control the ratio of boron and gallium in adulterant according to the initial electrical resistivity of the desired crystalline silicon reached.Preferably, when initial in the described polycrystalline silicon material in crucible, boron, gallium element the summation of atomic concentration be 5.7E+15～1.82E+18atoms/cm3。
In the present invention, described target resistivity is 1-3 Ω cm.Preferably, described target resistivity is 2-3 Ω cm.Described target resistivity can be 2 Ω cm, 2.3 Ω cm, 2.4 Ω cm, 2.5 Ω cm or 3 Ω cm, is not limited to this, can set according to the acceptable maximum resistivity of required silicon crystal.It is highly preferred that described target resistivity is 2.4 Ω cm.
In the present invention, described critical resistance rate is 1.0-3.0 Ω cm.Preferably, described critical resistance rate is 1.0-1.5 Ω cm.Described critical resistance rate can be 1.0 Ω cm, 1.1 Ω cm, 1.2 Ω cm, 1.3 Ω cm, 1.5 Ω cm, 1.8 Ω cm or 2 Ω cm.Can set according to the unacceptable minimum specific resistance of required silicon crystal.It is highly preferred that described critical resistance rate is 1.0 Ω cm or 1.5 Ω cm.
In the present invention, described target resistivity can more than or equal to described critical resistance rate.When described target resistivity is more than described critical resistance rate, when target yield is the same, described target resistivity is more big with the phase difference of described critical resistance rate, the number of times adding described polycrystalline silicon material in crucible in remaining silicon melt is also more few, often adding once described polycrystalline silicon material, the resistivity of the harsh crystal grown is recalled to target resistivity, along with the growth of crystal, its resistivity is down to again critical resistance rate, adds silicon material and is adjusted.And when described target resistivity closely or equal to described critical resistance rate time, the number of times adding described polycrystalline silicon material is also more many, is approximately equivalent to continuous charging.The resistivity of the crystal so grown is always positioned between critical resistance rate and target resistivity, and namely resistivity is kept essentially constant.Additionally, when being in close proximity to for set target resistivity or be equal to described critical resistance rate, the described polycrystalline silicon material added is necessary for liquid, can realize continuous charging.Especially for the boron element that segregation coefficient is bigger, with greater need for by continuous charging obtain resistivity high and be more evenly distributed, crystalline silicon that resistivity is more stable, be reduced as far as the fluctuation of light decay problem and the photoelectric transformation efficiency caused because resistivity is relatively uneven.
Wherein, when first time adds described polycrystalline silicon material, its addition Δ m1Calculate based on equation below:
Δm1=m0·K1, K1=(ρ0/ρ1-1) (1-X), wherein, ρ0For target resistivity, ρ1For critical resistance rate, X=n1/m0, m0The quality of silicon melt, n in crucible during for not starting long brilliant1For first time quality of the silicon melt of crystallization before reinforced.
Wherein, when i & lt adds described polycrystalline silicon material, described i is the integer more than or equal to 2, its addition Δ miIt is based on equation below to calculate:
Δmi=mi-1·Ki, Ki=(ρ0/ρ1-1)·(1-Xi), wherein, Xi=ni/mi-1, mi-1The quality of gallium silicon melt, wherein n is mixed in crucible after adding described polycrystalline silicon material for the last timeiAfter adding described polycrystalline silicon material for the last time to when previous add described polycrystalline silicon material time crystallization the quality mixing gallium silicon melt.
Wherein, when described adulterant is containing only when having gallium, whenFor m00.6-50 times time, stop reinforced, after treating the silicon melt crystallization in crucible, obtain crystalline silicon.It is preferably and works asFor m00.6-40 times time, stop reinforced.It is further preferred that work asFor m01-40 times time, stop reinforced.
Wherein, when described adulterant is containing only when having phosphorus, whenFor m00.2-30 times time, stop reinforced, after treating the silicon melt crystallization in crucible, obtain crystalline silicon.
It is further preferred that when described adulterant is containing only when having phosphorus, whenFor m01-20 times time, stop reinforced.
Wherein, when containing boron and gallium when described adulterant, whenFor m00.6-50 times time, stop reinforced, after treating the silicon melt crystallization in crucible, obtain crystalline silicon.It is preferably and works asFor m00.6-40 times time, stop reinforced.It is further preferred that work asFor m01-40 times time, stop reinforced.
It is understood that initial time crucible in the quality sum of polycrystalline silicon material and adulterant, namely equal to the quality m of silicon melt in when brilliant (do not start long) crucible time initial0；The gross mass of the described polycrystalline silicon material for adding in described crucible.
In the present invention, described mi-1After the second polycrystalline silicon material added for the last time melts, do not start to regrow the gross mass of the silicon melt in crucible before crystal.mi-1It is also equal to last time quality sum of the quality of remaining silicon melt and the last polycrystalline silicon material added in crucible when adding described polycrystalline silicon material.
When growing polycrystalline silicon ingot, the floor space of crucible is certain, or diameter during vertical pulling legal system silicon single crystal is certain, and solid fraction X is also equal to h1/H0,h1For the height of the silicon melt of crystallization, H before first time feed supplement0It is completely reformed into the full height corresponding to solid crystals silicon for the silicon melt in crucible time initial.For polycrystal silicon ingot, generally say long brilliant height, and for czochralski silicon monocrystal, it is common that refer to the length of crystal pulling.
Similarly, above-mentioned XiIt is also equal to hi/Hi-1,h1After adding described polycrystalline silicon material for the last time to when previous add described polycrystalline silicon material time the silicon melt of crystallization height, Hi-1After adding described polycrystalline silicon material for the last time, in crucible, silicon melt is completely reformed into the full height corresponding to solid crystals silicon.
Preferably, when described crystalline silicon is pulling of silicon single crystal, polycrystalline silicon material and adulterant are joined in the crucible of single crystal growing furnace；When described crystalline silicon is polycrystalline silicon ingot casting, polycrystalline silicon material and adulterant are joined in the crucible of crystalline silicon ingot casting furnace.In the present invention, the regulation and control of the growth parameter(s) of described crystalline silicon, method of the prior art can be adopted to carry out.
Preferably, when described crystalline silicon is czochralski silicon monocrystal, described adjustment crystalline silicon growth parameter(s), including:
Upper surface at described silicon melt places single crystal seed, controls the liquid level temperature in described crucible and the thermograde in described silicon melt, makes described silicon melt pull up growing single-crystal silicon by seed crystal.
Preferably, when described crystalline silicon is polycrystal silicon ingot, the mixture in described fusion crucible includes: regulate the heater power in described stove, in accordance with the order from top to bottom the mixture in fusion crucible gradually.
Preferably, when described crystalline silicon is polycrystal silicon ingot, described stove is ingot furnace, described adjustment crystalline silicon growth parameter(s), including:
The temperature controlled in described crucible is gradually increasing formation temperature gradient along vertical with described crucible bottom upwardly direction, makes described silicon melt start the long crystalline substance of bottom-up solidification.The heat-insulation cage opening described stove sidepiece can be coordinated to realize by reduction heater power simultaneously.
When adding described second polycrystalline silicon material, it is possible to suspend the aperture of described heat-insulation cage, readjust the power of heater, melt the polycrystalline silicon material being newly added in crucible gradually, treat its fusing completely, then start the growth of crystalline silicon.
Preferably, when preparing polycrystal silicon ingot, before loading polycrystalline silicon material and adulterant in crucible, the inner-wall spraying silicon nitride coating to described crucible, the thickness of described silicon nitride coating is 50-70 μm, and purity is more than 99.9%.The silicon nitride coating formed plays the effect of releasing agent, and the impurity within crucible can also be stoped to a certain extent to enter in cast main body.
Preferably, when preparing polycrystal silicon ingot, before loading polycrystalline silicon material and adulterant in crucible, it is possible to be equipped with seed crystal in the bottom of described crucible.In the process adding heat fusing, control heater speed makes the polycrystalline silicon material in crucible and adulterant all melt, seed portion fusing；When starting to grow crystal, reduce heater power and coordinate the heat-insulation cage opening described stove sidepiece simultaneously, make described silicon melt start to solidify long crystalline substance along the interface of bottom seed crystal.
The preparation method of the crystalline silicon described in first aspect present invention, in the process of growth crystal, when observing that the resistivity of crystalline silicon of growth reaches critical resistance rate, in crucible, just add a certain amount of polycrystalline silicon material, the concentration of the doped chemical in dilution silicon melt, crystalline silicon features (the afterbody of czochralski silicon monocrystal grown after avoiding, the head of the polycrystal silicon ingot of directional solidification) the concentration of doped chemical higher, resistivity is on the low side, doped chemical concentration difference in crystalline silicon can be made less, resistivity distribution uniform, meet the requirement of cell piece processing, improve crystalline silicon material utilization rate in preparing high performance solar batteries process, reduce the production cost of battery.
Secondly, said method is to add simple polycrystalline silicon material in the latter half of crystalline silicon grows, and and the element being not added with compensating mutually with original doped chemical (as original gallium compensated adding appropriate phosphorus) etc., one so that controlling resistivity, can not result in silicon crystal and there is part transoid (as become N-type by P type).
Moreover, containing single doped chemical in the crystalline silicon of present invention growth, or containing same type of doped chemical (be all alms giver, or be all acceptor), low light attenuation, high resistivity yield, resistivity evenness can be taken into account, the final photoelectric transformation efficiency improving solaode.
Second aspect, the invention provides a kind of crystalline silicon prepared by above-mentioned preparation method.
Advantages of the present invention will partly illustrate in the following description, and a part is apparent from according to description, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the axial distribution figure of the resistivity of three gallium doped monocrystaline silicon rods that the embodiment of the present invention 1 draws；
Fig. 2 is the axial distribution figure of the resistivity mixing gallium polycrystal silicon ingot that the embodiment of the present invention 2 prepares；
Fig. 3 is the axial distribution figure of the resistivity mixing gallium polycrystal silicon ingot that the embodiment of the present invention 3 prepares；
Fig. 4 is phosphorous doped polysilicon ingot (a) for preparing of the embodiment of the present invention 4 and the contrast of the axial distribution figure of the resistivity of phosphorous doped polysilicon ingot (b) in prior art；
Fig. 5 is the axial distribution figure of the resistivity mixing gallium polycrystal silicon ingot that the embodiment of the present invention 5 prepares；
Fig. 6 is the axial distribution figure of the resistivity of the polycrystal silicon ingot of the boron and gallium co-doped that the embodiment of the present invention 6 prepares；
Fig. 7 is the axial distribution figure of the resistivity of the polycrystal silicon ingot of single boron-doping that the embodiment of the present invention 7 prepares.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from embodiment of the present invention principle; can also making some improvements and modifications, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Embodiment one
The preparation method of a kind of gallium doped monocrystaline silicon, comprises the following steps:
1, reinforced: by the gallium of the polycrystalline silicon material of 120kg and 4.02g, (in the silicon material of every cubic centimetre, the atomic volume concentration of gallium is 6.9E+17atoms/cm3) put into the silica crucible of single crystal growing furnace, the model of described crucible is 24 cun of silica crucibles so that the target resistivity of czochralski silicon monocrystal head is 2.5 Ω cm；Described single crystal growing furnace is additionally provided with continuous feeding, in described continuous feeding, puts into the second melted polycrystalline silicon material；
2, under argon or nitrogen protection, by heating temperatures to 1425 DEG C-1600 DEG C, polycrystalline silicon material in fused quartz crucible and gallium, make gallium element fuse into formation silicon melt in polysilicon solution；
3, single crystal seed is placed at the upper surface of described silicon melt, control the liquid level temperature in described crucible and thermograde in liquid, technique carries out seeding, necking down, shouldering, isometrical, ending routinely, growth czochralski silicon monocrystal, wherein, the czochralski silicon monocrystal being 206mm with the growth diameter of 5cm/h；
4, when crystal growth length reaches 100cm, the melt of remaining 45Kg in crucible, now the resistivity of crystal reaches critical resistance rate 1.0 Ω cm, when namely the weight of crystal bar reaches 75kg, ending, complete a crystal bar；
5, keep above-mentioned fusion temperature 1425-1600 DEG C, utilize continuous feeding first time to add molten state second polycrystalline silicon material of 88kg in silicon melt remaining in crucible, the doping content of remaining gallium in dilution melt；After just feeding in raw material, the crystal resistivity of growth is adjusted to target resistivity 2.5 Ω cm, and (quality of the second polycrystalline silicon material that above-mentioned first time adds, can in second vice-minister's crystalline substance process, and in melt, gallium concentration maintains 6.9E+17～1.82E+18atoms/cm3Between, the resistivity of the silicon single crystal rod namely grown is between 1-2.5 Ω cm)
6, crystal pulling is continued by above-mentioned old process, when the boule wt drawn after first time is reinforced reaches 85kg, ending, complete secondary crystal bar；
7, second polycrystalline silicon material of 88kg is added again to described second time, continue crystal pulling, making the crystal resistivity of growth after just feeding in raw material be adjusted to target resistivity 2.5 Ω cm, now, altogether additional the second polycrystalline silicon material (176Kg) is in crucible time initial 1.47 times of mixture quality；Finally the silicon melt in silica crucible is all pulled out, finally finish up and cool down.
The different parts of the monocrystal rod of growth in the present embodiment being sampled, and tests the axial distribution of the resistivity of crystal, result is as shown in Figure 1.As can be seen from Figure 1, the resistivity of whole monocrystal rod (a) of first time crystal pulling gained, for the second time whole monocrystal rod (b) of crystal pulling gained is all at 1-2.5 Ω cm, the resistivity of the overwhelming majority of the monocrystal rod (c) of third time crystal pulling gained is all at 1-2.5 Ω cm, small part is lower than 1 Ω cm, on the whole, in three monocrystal rod of gained, the part by weight (i.e. yield) being between 1-2.5 Ω cm reaches 86%.Accordingly, with respect to the crystal (yield about 60%) not diluting gallium concentration gained in prior art again through interpolation polycrystalline silicon material, the ratio of its yield improves 43%.
At 1-2.5 Ω cm, resistivity in three monocrystal rod being partially fabricated silicon chip, and is finally made solaode, its photoelectric transformation efficiency is 20.2%, and light decay is reduced to 0.05%.
It should be noted that in the present embodiment, prepare monocrystal silicon for batch Czochralski growth methods, in the embodiment that other are feasible, it is also possible to prepare monocrystal silicon by continuous Czochralski growth methods.
The method provided in the embodiment of the present invention, for the gallium element that doping segregation coefficient is less, just can pass through in long brilliant process, add polycrystalline silicon material and dilute gallium concentration to realize the crystalline silicon that resistance qualification rate is higher, photo attenuation is low, and for the doped chemical (such as phosphorus, arsenic, indium) single containing other, and same type of multiple doped chemical (be all alms giver, or be all acceptor) is equally applicable.
Embodiment two
A kind of preparation method mixing gallium polycrystal silicon ingot, comprises the following steps:
1, reinforced: before reinforced, the silica crucible (internal diameter 840mm × 840mm) of G5 type being coated silicon nitride, the thickness of described silicon nitride coating is 50 μm, and purity is more than 99.99%；The gallium adulterant of the polycrystalline silicon material of 300kg and 10g is put into described silica crucible, and (in the silicon material of every cubic centimetre, the atomic volume concentration of gallium is 6.68E+17atoms/cm3) so that the target resistivity of the afterbody of polycrystal silicon ingot is 2.6 Ω cm；The described ingot furnace of ingot furnace is additionally provided with continuous feeding, in described continuous feeding, puts into the second melted polycrystalline silicon material；
2, fusing: utilize fork truck to transfer to ingot furnace in the crucible installing raw material, and ingot casting body of heater is carried out evacuation, injects argon and heat, controlling ingot furnace internal heater power makes in-furnace temperature be stepped up to 1520 DEG C, polycrystalline silicon material in fusion crucible and gallium adulterant gradually in accordance with the order from top to bottom, makes gallium element fuse in melted silicon；
3, the first vice-minister is brilliant: after polycrystalline silicon material and gallium adulterant are completely melt formation silicon melt, enter crystal growing stage, the long brilliant initial stage, quickly temperature is reduced to 1420 DEG C, coordinate subsequently and open heat-insulation cage, the bottom-up beginning of described silicon melt is made to solidify long crystalline substance, the polycrystal silicon ingot being wherein 840*840mm with the growth area of 1.5cm/h；
4, reinforced: when described silicon melt crystallizes to 12cm, namely the weight of the silicon melt of crystallization reaches 195kg, the quality of remaining silicon melt is 105Kg, now, the resistivity of crystal reaches critical resistance rate 1.0 Ω cm, utilize the polycrystalline silicon material that continuous feeding adds 195Kg in crucible, to make the resistivity of crystal reach target resistivity 2.6 Ω cm when second time starts long crystalline substance；Wherein, when the summation of additional the second polycrystalline silicon material (195Kg) is initial in crucible 0.65 times of mixture quality；
5, suspend the aperture of heat-insulation cage, again control heater power, make in-furnace temperature be stepped up to 1500 DEG C, melt the polycrystalline silicon material being newly added in crucible gradually；
6, the second vice-minister is brilliant: when the polycrystalline silicon material fusing being newly added is complete, after forming new silicon melt, reducing heater power, the heat-insulation cage of ingot furnace is opened in cooperation simultaneously, controls thermograde, makes the silicon melt in crucible continue to solidify long crystalline substance until long crystalline substance terminates；
7, the silicon ingot that long crystalline substance is completed is annealed, cools down.
It should be noted that the second polycrystalline silicon material in the present embodiment can also directly adopt liquid, it is possible to be heated into liquid in advance by other devices, then again water conservancy diversion in this continuous feeding.At this point it is possible to omit step 5.
The different parts of the polycrystal silicon ingot of directional solidification growth in the present embodiment being sampled, and tests the axial distribution of the resistivity of crystal, result is as shown in Figure 2.Figure it is seen that in the silicon ingot of directional solidification gained, the resistivity ratio (i.e. yield) being between 1-2.6 Ω .cm reaches 76%.
Embodiment three
A kind of preparation method mixing gallium polycrystal silicon ingot, comprises the following steps:
Wherein, step 1-3 is with embodiment 2；
4, first time is reinforced: when described silicon melt crystallizes to 12cm, namely the weight of the silicon melt of crystallization reaches 195kg, the quality of remaining silicon melt is 105Kg, now, the resistivity of crystal reaches critical resistance rate 1.0 Ω cm, utilize the polycrystalline silicon material that continuous feeding adds 195Kg in crucible, to make the resistivity of crystal reach target resistivity 2.6 Ω cm when second time starts long crystalline substance；
5, suspend the aperture of heat-insulation cage, again control heater power, make in-furnace temperature be stepped up to 1500 DEG C, melt the polycrystalline silicon material being newly added in crucible gradually；
6, the second vice-minister is brilliant: when the polycrystalline silicon material fusing being newly added is complete, after forming new silicon melt, reduces heater power, coordinates the heat-insulation cage opening ingot furnace simultaneously, control thermograde, makes the silicon melt in crucible continue to solidify long crystalline substance；Wherein, the quality of the second polycrystalline silicon material that first time adds, it is possible in second vice-minister's crystalline substance process, gallium concentration in silicon melt is controlled at 6.68E+17～1.82E+18atoms/cm3Between, the resistivity of the polycrystal silicon ingot namely grown is between 1-2.6 Ω cm；
7, second time is reinforced: when the resistivity of crystal reaches critical resistance rate 1.0 Ω cm, now, after first time is reinforced, the weight of the silicon melt of crystallization reaches 390kg, utilize the polycrystalline silicon material that continuous feeding adds 195Kg in crucible, to make the resistivity of crystal reach target resistivity 2.6 Ω cm when second time starts long crystalline substance；The gross weight (390Kg) of the second now additional polycrystalline silicon material is in crucible time initial 1.3 times of mixture quality；
8, suspend the aperture of heat-insulation cage, again control heater power, make in-furnace temperature be stepped up to 1500 DEG C, melt the polycrystalline silicon material being newly added in crucible gradually；
9, the long crystalline substance of third time: when the polycrystalline silicon material fusing being newly added is complete, after forming new silicon melt, reduces heater power, coordinate the heat-insulation cage opening ingot furnace simultaneously, control thermograde, makes the silicon melt in crucible continue to solidify long crystalline substance, until long crystalline substance terminates；；Wherein, the quality of the second polycrystalline silicon material that second time adds, it is possible in second vice-minister's crystalline substance process, gallium concentration in silicon melt is controlled at 5.7E+17～1.82E+18atoms/cm3Between, the resistivity of the polycrystal silicon ingot namely grown is between 1-2.6 Ω cm；
10, the silicon ingot that long crystalline substance is completed is annealed, cools down.
The different parts of the polycrystal silicon ingot of directional solidification growth in the present embodiment being sampled, and tests the axial distribution of the resistivity of crystal, result is as shown in Figure 2.Figure it is seen that in the silicon ingot of directional solidification gained, the resistivity ratio (i.e. yield) being between 1-2.6 Ω .cm reaches 82.6%.Comparing (yield about 60% between 1-3 Ω .cm) accordingly, with respect in prior art without the polycrystal silicon ingot of polycrystalline silicon material dilution gallium concentration gained, the ratio of its yield improves 37.7%.Additionally, for embodiment two, the present invention with the addition of a silicon material more in long brilliant process, and doped chemical gallium is served better diluting effect, and the ratio of the qualified resistivity of the crystal obtained is higher.
At the polysilicon block of 1-2.6 Ω cm, resistivity being made silicon chip, and is finally made solaode, its photoelectric transformation efficiency is 18.3%, and light decay is reduced to 0.01%.
Embodiment four
The preparation method of a kind of phosphorous doped polysilicon ingot, comprises the following steps:
1, reinforced: before reinforced, the silica crucible (internal diameter 840mm × 840mm) of G5 type being coated silicon nitride, the thickness of described silicon nitride coating is 55 μm, and purity is more than 99.99%；The 50g phosphorus silicon foundry alloy that the polycrystalline silicon material of 400kg and resistivity are 0.002 Ω cm is put into described silica crucible, the target resistivity making the afterbody of polycrystal silicon ingot is that (in the silicon material of every cubic centimetre, the atomic volume concentration of phosphorus is 4.3E+15atoms/cm to 3.0 Ω cm3)；The described ingot furnace of ingot furnace is additionally provided with continuous feeding, in described continuous feeding, puts into the second melted polycrystalline silicon material；
2, fusing: utilize fork truck to transfer to ingot furnace in the crucible installing raw material, and ingot casting body of heater is carried out evacuation, injects argon and heat, controlling ingot furnace internal heater power makes in-furnace temperature be stepped up to 1520 DEG C, polycrystalline silicon material in fusion crucible and adulterant gradually in accordance with the order from top to bottom, makes P elements fuse in melted silicon；
3, the first vice-minister is brilliant: when polycrystalline silicon material with after being completely melt containing phosphorus dopant to form silicon melt, enter crystal growing stage, the long brilliant initial stage, quickly temperature is reduced to 1420 DEG C, coordinate subsequently and open heat-insulation cage, the bottom-up beginning of described silicon melt is made to solidify long crystalline substance, the polycrystal silicon ingot being wherein 840*840mm with the growth area of 1.5cm/h；
4, reinforced: when described silicon melt crystallizes to 19.5cm, namely the weight of the silicon melt of crystallization reaches 320kg, now, the resistivity of crystal reaches critical resistance rate 1.0 Ω cm, utilize the polycrystalline silicon material that continuous feeding adds 148Kg in crucible, to make the resistivity of crystal reach target resistivity 3.0 Ω cm when second time has just started long crystalline substance, wherein, the quality of the second affiliated polycrystalline silicon material, can make phosphorus concentration in silicon melt control at 4.3E+15 to 1.3E+16atoms/cm as far as possible in second vice-minister's crystalline substance process3Between, make the resistivity of the polycrystal silicon ingot grown between 1-3 Ω cm；
5, suspend the aperture of heat-insulation cage, again control heater power, make in-furnace temperature be stepped up to 1500 DEG C, melt the polycrystalline silicon material being newly added in crucible gradually；
6, the second vice-minister is brilliant: when the polycrystalline silicon material fusing being newly added is complete, after forming new silicon melt, reducing heater power, the heat-insulation cage of ingot furnace is opened in cooperation simultaneously, controls thermograde, makes the silicon melt in crucible continue to solidify long crystalline substance until long crystalline substance terminates；
7, the silicon ingot that long crystalline substance is completed is annealed, cools down.
Similarly, the second polycrystalline silicon material in the present embodiment can also directly adopt liquid, it is possible to is heated into liquid in advance by other devices, then again water conservancy diversion in this continuous feeding.At this point it is possible to omit step 5.
In the present embodiment, additional the second polycrystalline silicon material (148Kg) is in crucible time initial 0.37 times of mixture quality.Prepared phosphorous doped polysilicon ingot is tested the axial distribution of its resistivity, for the technique effect of the prominent present invention, additionally provide when not adopting polycrystalline silicon material dilution phosphorus under equal conditions the resistivity distribution of phosphorous doped polysilicon ingot obtained by (directly all solidification is long brilliant until long crystalline substance terminates at the silicon melt of step 3 of the present embodiment).Result is as shown in Figure 4.
From fig. 4, it can be seen that the polycrystal silicon ingot that the present embodiment prepares is 91.7% (a) at the yield of 1-3 Ω cm.Relative to the polycrystal silicon ingot (yield is 80%) not diluting phosphorus concentration gained in prior art by adding polycrystalline silicon material, the ratio of its yield improves 14.6%.
Embodiment five
A kind of preparation method mixing gallium polycrystal silicon ingot, comprises the following steps:
1, reinforced: before reinforced, the silica crucible (internal diameter 840mm × 840mm) of G5 type being coated silicon nitride, the thickness of described silicon nitride coating is 50 μm, and purity is more than 99.99%；The gallium of the polycrystalline silicon material of 100kg and 5.06g being put into described silica crucible so that the initial electrical resistivity of the afterbody of polycrystal silicon ingot is 2.0 Ω cm, in the silicon material of every cubic centimetre, the atomic volume concentration of gallium is 8.68E+17atoms/cm3；The described ingot furnace of ingot furnace is additionally provided with continuous feeding, in described continuous feeding, puts into the second melted polycrystalline silicon material；
2, fusing: utilize fork truck to transfer to ingot furnace in the crucible installing raw material, and ingot casting body of heater is carried out evacuation, injects argon and heat, controlling ingot furnace internal heater power makes in-furnace temperature be stepped up to 1520 DEG C, polycrystalline silicon material in fusion crucible and gallium gradually in accordance with the order from top to bottom, makes gallium element fuse in melted silicon；
3, the first vice-minister is brilliant: after polycrystalline silicon material and gallium adulterant are completely melt formation silicon melt, enter crystal growing stage, the long brilliant initial stage, quickly temperature is reduced to 1420 DEG C, coordinate subsequently and open heat-insulation cage, the bottom-up beginning of described silicon melt is made to solidify long crystalline substance, the polycrystal silicon ingot being wherein 840*840mm with the growth area of 1.2cm/h；
4, reinforced: when described silicon melt crystallizes to 1.2cm, namely the weight of the silicon melt of crystallization reaches 20kg, now, the resistivity of crystal reaches critical resistance rate 1.55 Ω cm, utilizing continuous feeding to add polycrystalline silicon material by the speed of 20Kg/h in crucible, this charging rate is substantially equal to rate of crystalline growth；The quality of the second polycrystalline silicon material being continuously added to, makes the polycrystal silicon ingot grown reach target resistivity 1.6 Ω cm；
5, monotroded continuous feeding quantity stops reinforced when reaching 700Kg, and the silicon ingot that long crystalline substance is completed is annealed, cools down.
What prepare in the present embodiment mixes in gallium polycrystal silicon ingot, and the yield at 1-2 Ω cm is 94%, and wherein, the stable ratio at the polycrystal silicon ingot of 1.55-1.6 Ω cm of resistivity is 87%.These results suggest that, the method for the embodiment of the present invention can obtain that resistance yield is higher, resistivity is distributed very stable crystalline silicon.
It should be noted that the resistivity (initial electrical resistivity 2.0 Ω cm) corresponding to adulterant in crucible when the target resistivity (1.6 Ω cm) in the present embodiment is not equal to initial.
Embodiment six
The preparation method of the polycrystal silicon ingot of a kind of boron and gallium co-doped, comprises the following steps:
1, reinforced: before reinforced, the silica crucible (internal diameter 840mm × 840mm) of G5 type being coated silicon nitride, the thickness of described silicon nitride coating is 55 μm, and purity is more than 99.99%；The polycrystalline silicon material of 400kg and borosilicate foundry alloy that the gallium of 6.08g, 19g resistivity are 0.002 Ω cm are put into described silica crucible, and (in the silicon material of every cubic centimetre, the atomic volume concentration of gallium is 3.0E+17atoms/cm3, boron atomic volume concentration be 2.7E+15atoms/cm3) so that the target resistivity of the afterbody of polycrystal silicon ingot is 3 Ω cm；The described ingot furnace of ingot furnace is additionally provided with continuous feeding, the second melted polycrystalline silicon material can be supplied with in described continuous feeding；
2, fusing: utilize fork truck to transfer to ingot furnace in the crucible installing raw material, and ingot casting body of heater is carried out evacuation, injects argon and heat, controlling ingot furnace internal heater power makes in-furnace temperature be stepped up to 1520 DEG C, polycrystalline silicon material in fusion crucible and adulterant gradually in accordance with the order from top to bottom, makes boron, gallium element fuse in melted silicon；
3, the first vice-minister is brilliant: after polycrystalline silicon material and adulterant are completely melt formation silicon melt, enter crystal growing stage, the long brilliant initial stage, quickly temperature is reduced to 1420 DEG C, coordinate subsequently and open heat-insulation cage, the bottom-up beginning of described silicon melt is made to solidify long crystalline substance, the polycrystal silicon ingot being wherein 840*840mm with the growth area of 1.5cm/h；
4, reinforced: when described silicon melt crystallizes to 19.5cm, namely the weight of the silicon melt of crystallization reaches 320kg, now, the resistivity of crystal reaches critical resistance rate 1.0 Ω cm, utilize the polycrystalline silicon material that continuous feeding adds 170Kg in crucible, to make the resistivity of crystal reach target resistivity 3 Ω cm when second time starts long crystalline substance；
5, suspend the aperture of heat-insulation cage, again control heater power, make in-furnace temperature be stepped up to 1500 DEG C, melt the polycrystalline silicon material being newly added in crucible gradually；
6, the second vice-minister is brilliant: when the polycrystalline silicon material fusing being newly added is complete, after forming new silicon melt, reducing heater power, the heat-insulation cage of ingot furnace is opened in cooperation simultaneously, controls thermograde, makes the silicon melt in crucible continue to solidify long crystalline substance until long crystalline substance terminates；
7, the silicon ingot that long crystalline substance is completed is annealed, cools down.
It can be seen that the polycrystal silicon ingot that the present embodiment prepares is 88.1% at the yield of 1-3 Ω cm.And not by adding the polycrystal silicon ingot of polycrystalline silicon material dilution boron, gallium concentration gained in prior art, its yield is 80%.
In addition, resistivity in the present embodiment and prior art is made silicon chip at the polysilicon block of 1-3 Ω cm, and it is finally made solaode, found that, the photoelectric transformation efficiency of the battery obtained by the silicon chip of this enforcement is 18.3%, light decay is reduced to 0.24%, and photoelectric transformation efficiency of the prior art is 18.2%, and light decay is 0.64%.
Embodiment seven
The preparation method of a kind of B-doped Polycrystalline Silicon ingot, comprises the following steps:
1, reinforced: before reinforced, the silica crucible (internal diameter 840mm × 840mm) of G5 type being coated silicon nitride, the thickness of described silicon nitride coating is 50 μm, and purity is more than 99.99%；By borosilicate foundry alloy that the polycrystalline silicon material of 100kg and 12g resistivity are 0.002 Ω cm, (in the silicon material of every cubic centimetre, the atomic volume concentration of boron is 6.95E+15atoms/cm3), the initial electrical resistivity making the afterbody of polycrystal silicon ingot is 2.5 Ω cm；The described ingot furnace of ingot furnace is additionally provided with continuous feeding, in described continuous feeding, puts into the second melted polycrystalline silicon material；
2, fusing: utilize fork truck to transfer to ingot furnace in the crucible installing raw material, and ingot casting body of heater is carried out evacuation, injects argon and heat, controlling ingot furnace internal heater power makes in-furnace temperature be stepped up to 1520 DEG C, polycrystalline silicon material in fusion crucible and boron dope agent gradually in accordance with the order from top to bottom, makes boron element fuse in melted silicon；
3, the first vice-minister is brilliant: after polycrystalline silicon material and boron dope agent are completely melt formation silicon melt, enter crystal growing stage, the long brilliant initial stage, quickly temperature is reduced to 1420 DEG C, coordinate subsequently and open heat-insulation cage, the bottom-up beginning of described silicon melt is made to solidify long crystalline substance, the polycrystal silicon ingot being wherein 840*840mm with the growth area of 1.5cm/h；
4, reinforced: when described silicon melt crystallizes to 2.1cm, namely the weight of the silicon melt of crystallization reaches 35kg, now, the resistivity of crystal reaches critical resistance rate 2.3 Ω cm, utilizing continuous feeding to add polycrystalline silicon material by the speed of 25Kg/h in crucible, this charging rate is substantially equal to rate of crystalline growth；The quality of the second polycrystalline silicon material being continuously added to, makes the polycrystal silicon ingot resistivity grown be basically stable at target resistivity 2.3 Ω cm；
5, stopping when continuous charging amount reaches 400Kg feeding in raw material, the silicon ingot that long crystalline substance is completed is annealed, cools down.
Prepared B-doped Polycrystalline Silicon ingot is tested the axial distribution of its resistivity, and result is as shown in Figure 7.
From figure 7 it can be seen that in the B-doped Polycrystalline Silicon ingot prepared in the present embodiment, the yield at 1-2.5 Ω cm is 100%, wherein, the ratio of the stable polycrystal silicon ingot near 2.3 Ω cm of resistivity is 84%.And not by adding the polycrystal silicon ingot of polycrystalline silicon material dilution phosphorus concentration gained in prior art, it is about 90% at the yield of 1-2.5 Ω cm, but resistivity is stable less in the ratio of a certain value.Compared to the solaode (its photo attenuation is about 0.8%) that B-doped Polycrystalline Silicon ingot of the prior art (1-2.5 Ω cm gradual change) is made, in the present embodiment, resistivity is basically stable at the light decay of the solaode that the B-doped Polycrystalline Silicon ingot of certain certain value is made also certain reduction, and its light decay is about 0.5%.
These results suggest that, the method for the embodiment of the present invention can obtain that resistance yield is higher, resistivity is distributed very stable crystalline silicon.
The method provided in the embodiment of the present invention, it is applicable not only to containing single doped chemical (such as gallium, phosphorus, arsenic, indium), also can realize, especially for the less element of segregation coefficient, the crystalline silicon that growth resistivity yield is higher, apply also for the preparation of crystalline silicon containing same type of multiple doped chemical.
Claims (10)
1. the preparation method of a crystalline silicon, it is characterised in that comprise the following steps:
Polycrystalline silicon material and adulterant are joined in the crucible of crystalline silicon ingot casting furnace or single crystal growing furnace；Described adulterant is containing one or more in the simple substance of doped chemical, alloy, oxide and nitride, and described doped chemical is boron and gallium, or is the one in boron, gallium and phosphorus；
Under protective gas exists, heating makes described polycrystalline silicon material and adulterant be completely melt to form silicon melt, regulate crystalline silicon growth parameter(s), described silicon melt is made to start to grow crystal, in the process of described growth crystal, when the resistivity of crystal reaches critical resistance rate, remaining silicon melt is added a certain amount of described polycrystalline silicon material in crucible and forms new silicon melt, the resistivity making the crystal grown by new silicon melt is adjusted target resistivity, described new silicon melt continues long crystalline substance, after treating the silicon melt crystallization in crucible, obtain the crystalline silicon of target yield, the target yield of described crystalline silicon is 75～99%；Wherein, in the process of described growth crystal, including adding described polycrystalline silicon material at least one times, described critical resistance rate is 1-3 Ω cm, and described target resistivity is 1-3 Ω cm, and described target resistivity is more than or equal to described critical resistance rate；Described yield refers in target crystal silicon, the accounting of resistivity crystalline silicon between 1-3 Ω cm.
2. preparation method as claimed in claim 1, it is characterised in that when the gross mass of the described polycrystalline silicon material added in described crucible reaches initial in crucible during K times of the quality sum of polycrystalline silicon material and adulterant, stop in described crucible reinforced, wherein,Wherein, Y0For target yield, Y0It is 75%～99%, Y1The yield of gained crystalline silicon when for not adding described polycrystalline silicon material.
3. preparation method as claimed in claim 2, it is characterised in that when described adulterant is containing only when having gallium or contain boron and gallium, described K is 0.6-50；
When described adulterant is containing only when having phosphorus, described K is 0.6-50；
When described adulterant is containing only when having boron, described K is 0.1-9.
4. preparation method as claimed in claim 1, it is characterised in that described crystalline silicon is czochralski silicon monocrystal or polycrystal silicon ingot.
5. preparation method as claimed in claim 1, it is characterized in that, described adulterant is gallium, gallium-silicon alloy, phosphorus pentoxide, phosphorus-silicon alloy, boron-silicon alloy, boron powder or the mixture for gallium and boron-silicon alloy, or it is gallium-silicon alloy and the mixture of boron-silicon alloy, or the mixture of gallium and boron powder, or the mixture of gallium-silicon alloy and boron powder.
6. preparation method as claimed in claim 5, it is characterised in that when described adulterant is containing only when having gallium, when initial in the described polycrystalline silicon material in crucible, the atomic volume concentration of gallium element is 5.7E+17～1.82E+18atoms/cm3；
When described adulterant is containing only when having phosphorus, when initial in the described polycrystalline silicon material in crucible, the atomic volume concentration of P elements is 4.37E+15～1.39E+16atoms/cm3；
When containing boron and gallium when described adulterant, when initial in the described polycrystalline silicon material in crucible, boron, gallium element the summation of atomic concentration be 5.7E+15～1.82E+18atoms/cm3；
When described adulterant is containing only when having boron, when initial in the described polycrystalline silicon material in crucible, the atomic volume concentration of boron element is 5.7E+15～1.82E+16atoms/cm3。
7. preparation method as claimed in claim 1, it is characterised in that when first time adds described polycrystalline silicon material, its addition Δ m1It is based on equation below to calculate:
Δm1=m0·K1, K1=(ρ0/ρ1-1) (1-X), wherein, ρ0For target resistivity, ρ1For critical resistance rate, X=n1/m0, m0The quality of silicon melt, n in crucible during for not starting long brilliant1For first time quality of the silicon melt of crystallization before reinforced.
8. preparation method as claimed in claim 7, it is characterised in that when i & lt adds described polycrystalline silicon material, described i is the integer more than or equal to 2, its addition Δ miIt is based on equation below to calculate:
Δmi=mi-1·Ki, Ki=(ρ0/ρ1-1)·(1-Xi), wherein, Xi=ni/mi-1, mi-1The quality of silicon melt, wherein n in crucible is added after described polycrystalline silicon material for the last timeiAfter adding described polycrystalline silicon material for the last time to when previous add described polycrystalline silicon material time the silicon melt of crystallization quality.
9. preparation method as claimed in claim 4, it is characterised in that when described crystalline silicon is polycrystal silicon ingot, described adjustment crystalline silicon growth parameter(s), including:
The temperature controlled in described crucible is gradually increasing formation temperature gradient along vertical with described crucible bottom upwardly direction, mixes gallium silicon melt and start the long crystalline substance of bottom-up solidification described in making；
When described crystalline silicon is czochralski silicon monocrystal, described adjustment crystalline silicon growth parameter(s), including:
Control the liquid level temperature in described crucible and the thermograde in described silicon melt, mix gallium silicon melt described in making and form gallium doped monocrystaline silicon growth by seed crystal pull-up.
10. the crystalline silicon prepared by the preparation method as described in any one of claim 1-9.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106222743A (en) * | 2016-09-19 | 2016-12-14 | 江西赛维Ldk太阳能高科技有限公司 | A kind of polycrystal silicon ingot and preparation method thereof and for preparing the ingot furnace of polycrystal silicon ingot |
| CN106222742A (en) * | 2016-09-12 | 2016-12-14 | 江西赛维Ldk太阳能高科技有限公司 | A kind of crystalline silicon and preparation method thereof |
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| CN106222742A (en) * | 2016-09-12 | 2016-12-14 | 江西赛维Ldk太阳能高科技有限公司 | A kind of crystalline silicon and preparation method thereof |
| CN106222742B (en) * | 2016-09-12 | 2019-01-29 | 江西赛维Ldk太阳能高科技有限公司 | A kind of crystalline silicon and preparation method thereof |
| CN106222743A (en) * | 2016-09-19 | 2016-12-14 | 江西赛维Ldk太阳能高科技有限公司 | A kind of polycrystal silicon ingot and preparation method thereof and for preparing the ingot furnace of polycrystal silicon ingot |
| CN106400108A (en) * | 2016-09-26 | 2017-02-15 | 江苏美科硅能源有限公司 | Technique for casting high-efficiency polycrystalline silicon ingot and silicon wafer by frequent nucleation |
| CN107541772A (en) * | 2017-07-17 | 2018-01-05 | 晶科能源有限公司 | A kind of preparation method for mixing algan single crystal rod |
| CN109537047A (en) * | 2019-01-03 | 2019-03-29 | 内蒙古中环光伏材料有限公司 | A kind of silicon material matching method improving monocrystalline quality |
| CN109735897A (en) * | 2019-03-22 | 2019-05-10 | 内蒙古中环光伏材料有限公司 | The method of material resistivity is remained in a kind of measuring and calculating Czochralski furnace |
| WO2020253032A1 (en) * | 2019-06-17 | 2020-12-24 | 宁夏隆基硅材料有限公司 | Crystal pulling method and single crystal furnace |
| CN114341407A (en) * | 2019-07-29 | 2022-04-12 | 环球晶圆股份有限公司 | Generation and use of dynamic state diagrams during growth of single crystal silicon ingots |
| CN110528066A (en) * | 2019-09-03 | 2019-12-03 | 宁夏隆基硅材料有限公司 | A kind of doping method, monocrystalline device and single crystal growing furnace |
| CN113026101A (en) * | 2019-12-25 | 2021-06-25 | 苏州阿特斯阳光电力科技有限公司 | Method for producing quasi-single crystal silicon ingot and quasi-single crystal silicon ingot |
| CN110965121A (en) * | 2019-12-31 | 2020-04-07 | 宁晋晶兴电子材料有限公司 | Low-attenuation polycrystalline silicon and preparation method thereof |
| EP3933076A1 (en) * | 2020-06-30 | 2022-01-05 | Jinko Green Energy (Shanghai) Management Co., Ltd | Method for preparing monocrystalline silicon and solar cell and photovoltaic module with monocrystalline silicon |
| CN114164489A (en) * | 2020-09-10 | 2022-03-11 | 宁夏隆基硅材料有限公司 | Method for manufacturing silicon single crystal rod |
| CN112176399A (en) * | 2020-09-21 | 2021-01-05 | 广东先导先进材料股份有限公司 | Preparation method and preparation device of single crystal containing doping elements |
| CN112195515B (en) * | 2020-09-29 | 2022-03-01 | 晶科能源股份有限公司 | Silicon crystal and preparation method thereof |
| CN112195515A (en) * | 2020-09-29 | 2021-01-08 | 晶科能源有限公司 | Silicon crystal and preparation method thereof |
| CN112680787B (en) * | 2021-03-17 | 2021-06-04 | 杭州晶宝新能源科技有限公司 | Growth method of monocrystalline silicon and monocrystalline silicon |
| CN112680787A (en) * | 2021-03-17 | 2021-04-20 | 杭州晶宝新能源科技有限公司 | Growth method of monocrystalline silicon and monocrystalline silicon |
| CN113862778A (en) * | 2021-09-30 | 2021-12-31 | 西安奕斯伟材料科技有限公司 | Crucible assembly, crystal pulling furnace and method for pulling monocrystalline silicon rod |
| CN114059152A (en) * | 2021-11-19 | 2022-02-18 | 包头美科硅能源有限公司 | Gallium element doping method for producing silicon single crystal rod by Czochralski method |
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