CN105887194A - Growth method of type-n monocrystalline silicon - Google Patents

Growth method of type-n monocrystalline silicon Download PDF

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Publication number
CN105887194A
CN105887194A CN201610364056.4A CN201610364056A CN105887194A CN 105887194 A CN105887194 A CN 105887194A CN 201610364056 A CN201610364056 A CN 201610364056A CN 105887194 A CN105887194 A CN 105887194A
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silicon
monocrystal silicon
doped chemical
monocrystal
time
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张俊宝
刘浦锋
宋洪伟
陈猛
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SHANGHAI ADVANCED SILICON TECHNOLOGY Co Ltd
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SHANGHAI ADVANCED SILICON TECHNOLOGY Co Ltd
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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
    • 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

Abstract

The invention provides a growth method of type-n monocrytalline silicon. The method comprises the steps that P is selected as a main doping element of the type-n monocrystalline silicon and added in the monocrystalline silicon growth process, Ga with the opposite effect is added as an auxiliary doping element of a semiconductor monocrystalline silicon to counteract the concentration increment of P in the monocrystalline silicon, and resistance fluctuations in the monocrystalline silicon growth process are controlled. Meanwhile, when the weight of the monocrystalline silicon meets the specific requirement, the auxiliary doping element Ga is added one or more times, the comprehensive concentration of the co-doping element in the monocrystalline silicon can be further precisely controlled, fluctuations of the electrical resistivity are reduced, the influence caused by volatility of the auxiliary doping element on the concentration of the doping element in melt can also be avoided, and the monocrystalline silicon growth yield can be improved.

Description

A kind of growing method of N-shaped monocrystal silicon
Technical field
The present invention relates to the growing method of a kind of monocrystalline growth with czochralski silicon, particularly to n-type semiconductor monocrystal silicon Growing method, controls resistivity fluctuation in particular by contrary electrical resistivity property, thus prepares narrow resistivity fluctuation monocrystal silicon Growing technology.
Background technology
In the manufacturing process of single crystal silicon semiconductor, that most-often used is vertical pulling method (Czochralski, abridge CZ), In vertical pulling method, polysilicon is to be filled in quartz glass crucibles (also referred to as silica crucible), then adds heat fusing and forms melted silicon, Immersing the backward upper rotary pulling of seed crystal in melted silicon, silicon, at the interface solidification and crystallization of seed crystal Yu molten solution, forms monocrystal silicon.
Using monocrystal silicon is power device prepared by substrate, it is desirable to the resistivity of monocrystal silicon is high, requires to use substrate simultaneously Resistance variations is little.Under normal circumstances, it is desirable to resistivity fluctuation less than ± 20%, strict requirement on devices resistivity fluctuation less than ± 15%.But when using CZ legal system to make N-shaped monocrystal silicon, doped chemical is less than 1 relative to the segregation coefficient of silicon single crystal, mixes in monocrystal silicon The concentration of miscellaneous element is lower than the concentration in melt.Along with the growth of crystal, the concentration of dopant in silicon melt gradually uprises, in phase Under homostasis segregation coefficient, dynamic segregation coefficient gradually rises, and in monocrystal silicon, the concentration of doped chemical gradually rises, and makes monocrystal silicon Axial resistivity be gradually lowered.Recently, silicon-based electronic devices, especially power device, it is desirable to monocrystal silicon has the narrowest Resistivity fluctuates, and therefore optimizes doping process minimizing resistivity fluctuation and just seems the most important.
Reducing to control monocrystal silicon resistivity, patent CN103282555, CN103046130 use codope lifting raw Long technique, adds two or more the element with contrary resistance characteristic, such as B and P in polycrystalline silicon raw material, subtracts Small resistor rate fluctuates.Patent 201510295534 uses crucible bottom to place Ga raw material, and disjunction fusing is added.But it is raw in reality In product, melted silicon a period of time to be stablized, liquation is in the case of free convection, and the raw material of crucible bottom will not be residual Stay, can all melt, it is impossible to play the effect being stepped up Ga.CN201310447431 uses and is coated with containing contrary at crucible internal walls The method of performance raw material coating, but in actual production, if coating is fusing into liquation during lifting, can be formed little Granule, granule can introduce defect in crystal and form polycrystalline.Have a strong impact on crystal mass.CN200910152971 contains in growth The solar energy level silicon single crystal of Ga, adds and P in growth course, but the volatility of Ga is the highest, by burn-off rate, stablize time Between, the impact of the many factors such as temperature of thermal field, it is impossible to accurately addition point and addition.Although two kinds of doped chemicals are used alone Resistivity all can be caused to reduce, but two kinds of doped chemicals have contrary electrical conduction mechanism, cancel out each other during co-doped.Such as In crystal growing process, while doped chemical B concentration increases, the concentration of doped chemical P also increases, and offsets doped chemical B concentration.Therefore resistivity can control within the specific limits.
But, the increase of the size of current monocrystal silicon and the increase of crystal length, the weight of crystal bar dramatically increases.So molten Body gross weight also dramatically increases, therefore the fusing time of polycrystalline silicon raw material, stabilization time, crystal growth time all with small size, The crystal growth technique of little weight there occurs significantly change.Simultaneously because the difference of the volatility of doped chemical, segregation coefficient, During actual product produces, these methods can realize reducing the purpose of resistivity fluctuation at the crystal growth initial stage.But it is as crystalline substance The growth of body, the segregation coefficient of two kinds of doped chemicals with contrary resistance characteristic is different, and enrichment rate in the melt is different, One of which element necessarily exceedes another kind of element, and resistivity is the most sensitive to the content of doped chemical, and doped chemical is comprehensive The minor variations of concentration can cause the drastically change of resistivity, and the control of resistivity can be deviateed rapidly initial value by codope, super Go out the scope of performance requirement.
Simultaneously because doped chemical degree of volatility is different, the doped chemical added in polycrystalline silicon raw material, at actual monocrystalline Concentration in silicon is more difficult to predict and control.
In order to solve the problems referred to above, patent of the present invention provides the growing technology of a kind of monocrystal silicon, is accurately controlled monocrystalline Codope element integrated concentration in silicon, reduces the fluctuation of resistivity, improves the yields of monocrystalline silicon growing.
Summary of the invention
It is an object of the invention to provide a kind of N-shaped crystal for straight drawing monocrystal growth method, monocrystal silicon is from head to afterbody Resistivity fluctuation is little, and the volatility of secondary doped chemical can be avoided the impact of doped chemical concentration in melt simultaneously.
In order to reach the above object, present invention process technology is to be realized by the following method: select P(phosphorus) as N-shaped The main doped chemical of single crystal silicon semiconductor, selects the Ga(gallium with adverse effect) as single crystal silicon semiconductor pair doped chemical, Resistivity requirement according to monocrystal silicon, obtains the curing degree of monocrystal silicon, and adds when monocrystal silicon reaches required curing degree Ga。
Further, the method adding Ga for the first time is characterised by,
The first step, determines the initial incremental amount of P
The growing method of monocrystal silicon of the present invention, selects P as the main doped chemical of n-type semiconductor monocrystal silicon.According to monocrystal silicon Resistivity requires to provide maximum resistance rate Rsi-maxWith lowest resistivity Rsi-min.According to maximum resistance rate Rsi-maxRequirement, determines P doping content C in initial polysiliconP0, and according to formula according to lowest resistivity Rsi-maxRequirement draws secondary doped chemical addition point Time curing degree.
Resistivity R of monocrystal siliconsiWith the relation of doped chemical total concentration C it is:
(1)
In formula, RsiFor the resistivity of monocrystal silicon, unit be Ω, C be doped chemical total concentration in monocrystal silicon, unit is atom/g. A is constant, value 1.84 × 1015。
Second step, determines the first time addition point S of Ga1。
At the monocrystalline silicon growing initial stage, P is added in polycrystalline silicon raw material, the concentration C of the P in monocrystal siliconPAlong with monocrystal silicon Growing and change, its relation is:
(2)
(3)
(4)
(5)
In formula (3), S is the curing degree of monocrystal silicon, CP0 lFor the initial concentration of P, C in silicon meltP lFor the reality of P in silicon melt Time concentration, GcrystalFor the monocrystal silicon weight grown, GtotalFor add polysilicon gross weight, rcFor silica crucible half Footpath, rSiFor the radius of silicon single crystal bar, v is pull rate.
Along with crystal growth, the concentration C of the P in monocrystal siliconPIncrease along with the growth of monocrystal silicon, the resistivity of monocrystal silicon RsiIt is gradually lowered.According to lowest resistivity Rsi-minDoped chemical maximum concentration C in monocrystal silicon is determined with formula (1)0, due to Now only having P doped chemical in monocrystal silicon, the P's that in monocrystal silicon now, doped chemical total concentration is in monocrystal silicon is dense Degree, so that it is determined that the weight of curing degree and now monocrystal silicon.The weight stamp of monocrystal silicon now is Gcrystal-1, consolidating now Rate is labeled as S1, doped chemical total concentration is designated as C1, the concentration markers of the P in monocrystal silicon is CP1.When the weight of monocrystal silicon reaches Then Gcrystal-1, add secondary doped chemical Ga.Crystal growing process adds secondary doped chemical at this moment, doping can be avoided The volatility of element is on the impact of doped chemical concentration in melt.
3rd step determines first time addition C of GaGa10。
Secondary doped chemical Ga addition in the melt is CGa10, wherein,
(6)
In formula (5), CGa10For the secondary the most primary addition of doped chemical Ga, unit is atom/g.C0For polysilicon Middle initial dopant element total concentration, owing to only having P, C in initial polysilicon0With CP0Identical.C1 adds and adds pair doping for the first time Doped chemical total concentration in fused solution during element Ga.After secondary doped chemical Ga adds, the resistivity of monocrystal silicon returns to close to High resistivity Rsi-max。
Patent of the present invention is characterised by, when the weight of monocrystal silicon arrives Gcrystal-1Time, add secondary doped chemical Ga.This Patent of invention is further characterized in that secondary doped chemical Ga adds with the form of Si-Ga alloy, and in Si-Ga alloy, the amount containing Ga is 0.1wt%.In Si-Ga alloy, the too low alloy amount that then adds of the amount containing Ga is many, and burn-off rate is low, and solid affects crystal mass；Too high then Locally Ga too high levels, volatilization is big, and concentration is inaccurate.
Further, patent of the present invention is characterised by, can add secondary doped chemical Ga with one or many.
Second time adds the mode of Ga and is characterised by
The first step, determines that the doped chemical total concentration in monocrystal silicon is along with the variation relation of crystal growth
After secondary doped chemical Ga adds, the doped chemical total concentration in monocrystal silicon continues to increase along with crystal growth, it is characterized by:
(7)
(8)
(9)
(10)
(11)
In formula, S is the curing degree of monocrystal silicon, CGa1For the concentration of Ga in monocrystal silicon after addition Ga for the first time.Cl Ga1For adding for the first time Enter after Ga the real-time concentration of Ga, C in silicon meltl Ga10For the initial concentration of Ga, S in silicon melt after addition Ga for the first timeGa1For Add the curing degree of Ga for the first time.Doped chemical total concentration C in monocrystal silicon continues to be further added by along with crystal growth.
Second step, determines the addition point S of second time Ga2
In the growth course of monocrystal silicon, doped chemical total concentration C in monocrystal silicon continues to be further added by along with crystal growth, then root Lowest resistivity R is determined according to formula (1)si-min, and monocrystal silicon weight.When monocrystal silicon reaches lowest resistivity R againsi-minTime, The weight stamp of monocrystal silicon now is Gcrystal-2, curing degree now is labeled as S2, doped chemical total concentration is designated as C2.Work as list The weight of crystal silicon reaches Gcrystal-2Time, second time adds secondary doped chemical Ga.
3rd step, determines addition C of second time GaGa20
In the growth course of monocrystal silicon, secondary doped chemical Ga second time addition in the melt is CGa20.It is characterised by,
(12)
In formula, CGa2Secondary doped chemical Ga second time addition in the melt, unit is atom/g.Secondary doped chemical Ga adds After, the resistivity of monocrystal silicon returns to close to maximum resistance rate Rsi-max。
4th step, determines the change again with crystal growth of the doped chemical total concentration in monocrystal silicon
In the growth course of monocrystal silicon, after secondary doped chemical Ga adds, the doped chemical total concentration in monocrystal silicon again with Crystal growth continues to increase, and it is characterized by:
(13)
(14)
(15)
(16)
(17)
In formula, S is the curing degree of monocrystal silicon, CGa2The concentration of Ga in monocrystal silicon is introduced after adding Ga for second time.Cl Ga2It is second The real-time concentration of Ga, C in silicon melt after secondary addition Gal Ga20The initial concentration of Ga in silicon melt is added after Ga for second time, SGa2The curing degree of Ga is added for second time.
Further, in the growth course of monocrystal silicon, if the resistivity of monocrystal silicon reaches lowest resistivity again Rsi-min, it is also possible to continuously add sub-control element Ga in the melt.Its addition is carried out as stated above.
Further, in the growth course of monocrystal silicon, when curing degree reaches more than 90%, although resistivity reaches Small resistor rate Rsi-min, but do not add control element Ga.Can ensure that yields reaches more than 85%.
The monocrystalline silicon growing method of the present invention, select P as the main doped chemical of n-type semiconductor monocrystal silicon, and at monocrystalline Add during silicon growth, there is the Ga of adverse effect as single crystal silicon semiconductor pair doped chemical, offset P concentration in monocrystal silicon Increment, controls the resistance fluctuation during monocrystalline silicon growing.Simultaneously when the weight of monocrystal silicon reaches particular requirement, once or many Secondary doped chemical Ga of secondary addition, can the most accurately control the codope element integrated concentration in monocrystal silicon, reduce resistivity Fluctuation, it is also possible to avoid the volatility of secondary doped chemical on the impact of doped chemical concentration in melt, improve monocrystalline silicon growing Yields.
Accompanying drawing explanation
Fig. 1 be in monocrystalline silicon growing of the present invention doped chemical concentration with crystal growth variation relation.
Fig. 2 is monocrystalline silicon growing embodiment 1 schematic diagram of the present invention.
Fig. 3 is monocrystalline silicon growing embodiment 2 schematic diagram of the present invention.
Fig. 4 is monocrystalline silicon growing comparative example 2 schematic diagram of the present invention.
Detailed description of the invention
Embodiment 1
Use the N-shaped silicon single crystal rod in 8 inches of<100>directions of CZ method growth.The polycrystalline silicon raw material of 120kg is added in silica crucible And phosphorus, resistivity target value 60-100 Ω, i.e. maximum resistance rate Rsi-maxIt is 100 Ω, lowest resistivity Rsi-minIt is 60 Ω.By formula (1) by maximum resistance rate Rsi-maxThe initial concentration drawing phosphorus is 5.9 × 1013Atom/g, simultaneously by lowest resistivity Rsi-minMeter When calculation draws secondary doped chemical addition point, curing degree is 0.54.
In being embodied as, under the protection of noble gas, remove the absorption oxygen in raw material.Open heater to be progressively warmed up to Raw material is made to be completely melt for more than 1420 DEG C.Carry out seeding, shouldering, turn shoulder according to conventional crystalline growth parameter(s), enter the isometrical stage. When curing degree reaches 0.54, when both the weight of crystal bar reaches 65kg, adding the Ga of 10mg, Adding Way is measured containing Ga for adding 10g It it is the Si-Ga alloy of 0.1%.When crystal weight reaches 105kg, entering ending, final Total crystal weight is 111kg.
Cutting multiple detection resistance from crystal bar, the resistivity of crystal bar head is 99 Ω, then as prolonging rearwardly Stretching, resistivity declines, and before Ga adds, resistivity is 61 Ω.After adding Ga, resistance rises to 97 Ω, declines subsequently, at afterbody is 58Ω
Embodiment 2
Use the N-shaped silicon single crystal rod in 8 inches of<100>directions of CZ method growth.The polycrystalline silicon raw material of 120kg is added in silica crucible And phosphorus, resistivity target value 70-100 Ω, i.e. maximum resistance rate Rsi-maxIt is 100 Ω, lowest resistivity Rsi-minIt is 70 Ω.By formula (1) by maximum resistance rate Rsi-maxThe initial concentration drawing phosphorus is 5.9 × 1013Atom/g, simultaneously by lowest resistivity Rsi-minMeter Calculation show that secondary doped chemical needs twice addition, and during addition point, curing degree is respectively 0.40 and 0.68.
In being embodied as, under the protection of noble gas, remove the absorption oxygen in raw material.Open heater to be progressively warmed up to Raw material is made to be completely melt for more than 1420 DEG C.Carry out seeding, shouldering according to conventional crystalline growth parameter(s), turn shoulder, entrance grade stage. When curing degree reaches 0.40, when both the weight of crystal bar reaches 48kg, adding the Ga of 7.9mg for the first time, Adding Way is for adding 7.9g amount containing Ga is the Si-Ga alloy of 0.1%.When curing degree reaches 0.68, when both the weight of crystal bar reaches 81.6kg, add The Ga of 4.2mg, Adding Way is to add the Si-Ga alloy that 4.2g amount containing Ga is 0.1%.
When crystal weight reaches 105kg, entering ending, final Total crystal weight is 112kg.
Cutting multiple detection resistance from crystal bar, the resistivity of crystal bar head is 99 Ω, then as prolonging rearwardly Stretching, resistivity declines, and before Ga adds for the first time, resistivity is 71 Ω.After adding Ga, resistance rises to 98 Ω, declines subsequently, Before Ga second time adds, resistivity is 71 Ω.After adding Ga, resistance rises to 97 Ω, declines subsequently, is 55 Ω at afterbody.
Embodiment 3
Use the N-shaped silicon single crystal rod in 8 inches of<100>directions of CZ method growth.The polycrystalline silicon raw material of 120kg is added in silica crucible And phosphorus, resistivity target value 80-100 Ω, i.e. maximum resistance rate Rsi-maxIt is 100 Ω, lowest resistivity Rsi-minIt is 80 Ω.By formula (1) by maximum resistance rate Rsi-maxThe initial concentration drawing phosphorus is 5.9 × 1013Atom/g, simultaneously by lowest resistivity Rsi-minMeter Calculation show that secondary doped chemical needs four times and adds, and during addition point, curing degree is respectively 0.25,0.47,0.63 and 0.78.
In being embodied as, under the protection of noble gas, remove the absorption oxygen in raw material.Open heater to be progressively warmed up to Raw material is made to be completely melt for more than 1420 DEG C.Carry out seeding, shouldering, turn shoulder according to conventional crystalline growth parameter(s), enter the isometrical stage. When curing degree reaches 0.25, when both the weight of crystal bar reaches 30kg, adding the Ga of 5.1mg for the first time, Adding Way is for adding 5.1g amount containing Ga is the Si-Ga alloy of 0.1%.When curing degree reaches 0.47, when both the weight of crystal bar reaches 56kg, second time adds Entering the Ga of 3.6mg, Adding Way is to add the Si-Ga alloy that 3.6g amount containing Ga is 0.1%.When curing degree reaches 0.63, both crystal bars Weight when reaching 75kg, third time adds the Ga of 2.5mg, and Adding Way is to add the Si-Ga that 2.5g amount containing Ga is 0.1% to close Gold.When curing degree reaches 0.78, when both the weight of crystal bar reaches 93.5kg, the Ga that the 4th time adds 1.5mg, Adding Way is for adding Enter the Si-Ga alloy that 1.5g amount containing Ga is 0.1%.
When crystal weight reaches 105kg, entering ending, final Total crystal weight is 110kg.
Cutting multiple detection resistance from crystal bar, the resistivity of crystal bar head is 99 Ω, then as prolonging rearwardly Stretching, resistivity declines.Before Ga adds for the first time, resistivity is 83 Ω, and after adding Ga, resistance rises to 99 Ω, declines subsequently.? Before Ga second time adds, resistivity is 82 Ω.After adding Ga, resistance rises to 97 Ω, declines subsequently.Electricity before Ga third time adds Resistance rate is 81 Ω, and after adding Ga, resistance rises to 97 Ω, declines subsequently.Before Ga adds for the 4th time, resistivity is 81 Ω.Add After Ga, resistance rises to 96 Ω, declines subsequently.It is 50 Ω at afterbody.Yields 88%.
Comparative example 1
Use the N-shaped silicon single crystal rod in 8 inches of<100>directions of CZ method growth.The polycrystalline silicon raw material of 120kg is added in silica crucible And phosphorus, it is added without secondary doped chemical and is controlled.Resistivity target value 70-100 Ω.
In being embodied as, under the protection of noble gas, remove the absorption oxygen in raw material.Open heater to be progressively warmed up to Raw material is made to be completely melt for more than 1420 DEG C.Carry out seeding, shouldering, turn shoulder according to conventional crystalline growth parameter(s), enter the isometrical stage. When crystal weight reaches 105kg, entering ending, final Total crystal weight is 110kg.
Cutting multiple detection resistance from crystal bar, the resistivity of crystal bar head is 99 Ω, then as prolonging rearwardly Stretching, resistivity declines, and is 25 Ω at afterbody.Yields is less than 30%.
Comparative example 2
Use the N-shaped silicon single crystal rod in 8 inches of<100>directions of CZ method growth.The polysilicon adding 120kg in silica crucible is former Material, is simultaneously introduced phosphorus and gallium, resistivity target value 60-100 Ω in polycrystalline silicon raw material.
In melt, the original concentration of P is 1.6 × 1014Atom/g, in order to reach the electrical resistivity range of requirement, corresponds Ga concentration in the melt be 3.5 × 1015atom/g。
After crystal growth, Resistivity testing shows, in crystal bar head about 5kg position, the resistivity of monocrystal silicon is 74 Ω.? About 40kg position, the resistivity of monocrystal silicon is 64 Ω.In about 50kg position, the resistivity of monocrystal silicon reduces to 59 Ω, at about 105kg Position, the resistivity of monocrystal silicon has been 15 Ω.Yields is less than 50%.
In this example, the Ga being simultaneously introduced with polysilicon, in actual production, effective Ga content is equivalent to is 3.1 × 1015Atom/g, has a difference with addition, and about 0.5 × 1015atom/g.Produce this difference to be because Ga and easily wave Send out.And it is the most rambunctious that the most small amount adds fashionable in initial feed, but just it is because the most small difference, but may be used To cause the change that resistivity is the biggest.Therefore explanation uses doped chemical the most secondary with polysilicon to carry out co-controlling is to be difficult to Realize.

Claims (7)

1. a crystal for straight drawing monocrystal growth method, the mainly growing method of n-type semiconductor monocrystal silicon, select P as N-shaped half The main doped chemical of conductor monocrystal silicon, selects have the Ga of adverse effect as single crystal silicon semiconductor pair doped chemical, its feature It is, according to the resistivity requirement of monocrystal silicon, obtains the curing degree of monocrystal silicon, and when monocrystal silicon reaches required curing degree Add Ga.
Crystal for straight drawing monocrystal growth method the most according to claim 1, it is characterised in that reach required at monocrystal silicon In crucible, add Ga during curing degree for the first time, and add Ga's for the first time method particularly includes:
(1) first step, determines the doping of P
Resistivity according to monocrystal silicon requires to provide maximum resistance rate Rsi-maxWith lowest resistivity Rsi-min, and according to formula (1) root According to maximum resistance rate Rsi-maxRequirement, determines P doping content C in initial polysiliconP0, and according to formula (2), (3), (4), (5) according to lowest resistivity Rsi-maxRequire to draw curing degree during secondary doped chemical addition point, wherein,
Resistivity R of monocrystal siliconsiWith the relation of doped chemical total concentration C it is:
(1)
In formula (1), RsiFor the resistivity of monocrystal silicon, unit be Ω, C be doped chemical total concentration in monocrystal silicon, unit is atom/ G, a are constant, value 1.84 × 1015；
(2) second step, determines the first time addition point S of Ga1
At the monocrystalline silicon growing initial stage, P is added in polycrystalline silicon raw material, the concentration C of the P in monocrystal siliconPAlong with monocrystal silicon growth and Changing, its relation is:
(2)
(3)
(4)
(5)
In formula (3), S is the curing degree of monocrystal silicon, CP0 lFor the initial concentration of P, C in silicon meltP lFor the reality of P in silicon melt Time concentration, GcrystalFor the monocrystal silicon weight grown, GtotalFor add polysilicon gross weight, rcFor silica crucible half Footpath, rSiFor the radius of silicon single crystal bar, v is pull rate,
According to lowest resistivity Rsi-minDoped chemical maximum concentration C in monocrystal silicon is determined with formula (1)0, the weight mark of monocrystal silicon It is designated as Gcrystal-1, curing degree now is labeled as S1, doped chemical total concentration is designated as C1, the concentration markers of the P in monocrystal silicon is CP1；
The G when the weight of monocrystal silicon reachescrystal-1, add secondary doped chemical Ga；
(3) the 3rd steps, determine first time addition C of GaGa10
Secondary doped chemical Ga addition in the melt is CGa10, wherein,
(6)
In formula (5), CGa10For secondary doped chemical Ga first time addition in the melt, unit is atom/g, C0For in polysilicon Initial dopant element total concentration, owing to only having P, C in initial polysilicon0With CP0Identical, C1 adds pair doping for the first time for adding Doped chemical total concentration in fused solution during element Ga, after secondary doped chemical Ga adds, the resistivity of monocrystal silicon returns to close to High resistivity Rsi-max。
Crystal for straight drawing monocrystal growth method the most according to claim 1, is characterised by that secondary doped chemical Ga is with Si-Ga alloy Form add, in Si-Ga alloy, the amount containing Ga is for 0.1wt%.
4., according to the crystal for straight drawing monocrystal growth method described in Claims 2 or 3, secondary doped chemical can be added with one or many Ga, it is characterised in that whenever monocrystal silicon reaches lowest resistivity R againsi-minShi Zaici adds secondary doped chemical Ga, with this type of Pushing away, when resistivity reaches minimum, one or many adds secondary doped chemical Ga.
Crystal for straight drawing monocrystal growth method the most according to claim 4, it is characterised in that reach required at monocrystal silicon During curing degree in crucible second time add Ga, and method particularly as follows:
(1) first step, determines that the doped chemical total concentration in monocrystal silicon is along with the variation relation of crystal growth
After secondary doped chemical Ga adds, the doped chemical total concentration in monocrystal silicon continues to increase, wherein along with crystal growth:
(7)
(8)
(9)
(10)
(11)
In formula, S is the curing degree of monocrystal silicon, CGa1For the concentration of Ga, C in monocrystal silicon after addition Ga for the first timel Ga1For adding for the first time Enter after Ga the real-time concentration of Ga, C in silicon meltl Ga10For the initial concentration of Ga, S in silicon melt after addition Ga for the first timeGa1For Adding the curing degree of Ga for the first time, doped chemical total concentration C in monocrystal silicon continues to be further added by along with crystal growth；
(2) second step, determines the addition point S of second time Ga2
In the growth course of monocrystal silicon, doped chemical total concentration C in monocrystal silicon continues to be further added by along with crystal growth, then root Lowest resistivity R is determined according to formula (1)si-min, and monocrystal silicon weight, when monocrystal silicon reaches lowest resistivity R againsi-minTime, The weight stamp of monocrystal silicon now is Gcrystal-2, curing degree now is labeled as S2, doped chemical total concentration is designated as C2, work as list The weight of crystal silicon reaches Gcrystal-2Time, second time adds secondary doped chemical Ga；
(3) the 3rd steps, determine addition C of second time GaGa20
In the growth course of monocrystal silicon, secondary doped chemical Ga second time addition in the melt is CGa20, wherein,
(12)
In formula, CGa2Secondary doped chemical Ga second time addition in the melt, unit is atom/g, and secondary doped chemical Ga adds After, the resistivity of monocrystal silicon returns to close to maximum resistance rate Rsi-max；
(4) the 4th steps, determine the change again with crystal growth of the doped chemical total concentration in monocrystal silicon
In the growth course of monocrystal silicon, after secondary doped chemical Ga adds, the doped chemical total concentration in monocrystal silicon again with Crystal growth continues to increase, wherein:
(13)
(14)
(15)
(16)
(17)
In formula, S is the curing degree of monocrystal silicon, CGa2The concentration of Ga, C in monocrystal silicon is introduced after adding Ga for second timel Ga2It is second The real-time concentration of Ga, C in silicon melt after secondary addition Gal Ga20The initial concentration of Ga in silicon melt is added after Ga for second time, SGa2The curing degree of Ga is added for second time.
Crystal for straight drawing monocrystal growth method the most according to claim 2, it is characterised in that along with the growth of monocrystal silicon, its If resistivity reaches lowest resistivity R againsi-min, it is also possible to continuously add sub-control element Ga in the melt.
Crystal for straight drawing monocrystal growth method the most according to claim 5, it is characterised in that along with the growth of monocrystal silicon, its If resistivity reaches lowest resistivity R againsi-min, it is also possible to continuously add sub-control element Ga in the melt.
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CN109023509A (en) * 2018-08-31 2018-12-18 包头美科硅能源有限公司 A method of preparing solar level n type single crystal silicon
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US11408090B2 (en) 2019-04-18 2022-08-09 Globalwafers Co., Ltd. Methods for growing a single crystal silicon ingot using continuous Czochralski method
US11111597B2 (en) 2019-09-13 2021-09-07 Globalwafers Co., Ltd. Methods for growing a nitrogen doped single crystal silicon ingot using continuous Czochralski method
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