CN104711675A - Phosphorus, arsenic and antimony co-doped N-type heavily-doped Czochralski silicon single crystal and silicon epitaxial wafer thereof - Google Patents
Phosphorus, arsenic and antimony co-doped N-type heavily-doped Czochralski silicon single crystal and silicon epitaxial wafer thereof Download PDFInfo
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- CN104711675A CN104711675A CN201510083673.2A CN201510083673A CN104711675A CN 104711675 A CN104711675 A CN 104711675A CN 201510083673 A CN201510083673 A CN 201510083673A CN 104711675 A CN104711675 A CN 104711675A
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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
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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
- C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
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Abstract
The invention discloses a phosphorus, arsenic and antimony co-doped N-type heavily-doped Czochralski silicon single crystal and a silicon epitaxial wafer thereof. The phosphorus, arsenic and antimony co-doped N-type heavily-doped Czochralski silicon single crystal takes phosphorus as the main doping element, and either or both of arsenic and antimony as auxiliary doping elements, the concentration of phosphorus is larger than or equal to 4.6*10<19>/cm<3>, phosphorus accounts for more than or equal to 60% of the doping elements, and the auxiliary doping elements accounts for 0.1-40% of the doping elements. The phosphorus, arsenic and antimony co-doped N-type heavily-doped Czochralski silicon single crystal can eliminate or remarkably reduce slip lines caused by lattice mismatching in the silicon epitaxial wafer, and can effectively reduce or eliminate mismatched dislocation lines generated when an epitaxial layer is grown on a polished wafer formed by processing of the N-type heavily-doped Czochralski silicon single crystal with high doping concentration; while the problems are solved, widening of a transition zone in a semi-conductor device after a high-temperature process is prevented; the industry practice that two or more of phosphorus, arsenic and antimony in a silicon single crystal cannot serve as dopants at the same time is changed.
Description
Technical field
The present invention relates to czochralski silicon monocrystal field.
Background technology
By the adulterated arsenic vertical gulling silicon monocrystalline that take arsenic as main doped element, (concentration of arsenic is for 1.2 × 10
19-3.4 × 10
19/ cm
3) manufacture silicon polished, then this polished section is manufactured the epitaxial wafer that electrical resistivity of epitaxy is greater than 1 Ω .cm, this epitaxial wafer after the high temperature working processes of semiconducter device in the distribution of vertical surface direction epilayer resistance rate as shown in Figure 1.Resistivity between silicon epitaxy layer and polished substrate region is from high to low called as extension zone of transition.If arsenic removal is outward also containing a small amount of phosphorus in polished substrate, the extension zone of transition that the extension zone of transition of its correspondence is just corresponding than the polished substrate only containing arsenic is wide, and the concentration of phosphorus is greater than 5 × 10
14/ cm
3time it will obviously show the impact of extension zone of transition.After pyroprocess, extension zone of transition is wider means that the net thickness of epitaxial film is less, the voltage breakdown of device is lower, and this will make great efforts in device manufacturing processes to be avoided.Same problem can be there is when being mixed into a small amount of phosphorus or arsenic in reblended antimony czochralski silicon monocrystal.Because worry that the introducing of other doping agent can reduce the voltage breakdown of device, what mix during current manufacture N-type adulterating vertical pulling silicon monocrystalline is all single doping agent, namely chooses any one kind of them as required to be incorporated in czochralski silicon monocrystal as doped element that (concentration is greater than 1 × 10 in phosphorus, arsenic, antimony
18/ cm
3), when mixing any one of aforementioned three kinds of doping agents, the concentration of the other two kinds of dopant elements of strict restriction in grown czochralski silicon monocrystal, their concentration of technical indicator general requirement is less than 1 × 10
14/ cm
3.Also nobody manufactures and sells the N-type adulterating vertical pulling silicon monocrystalline of phosphorus arsenic antimony codoped and the silicon epitaxial wafer by its processing at present, and also nobody proposed relevant theory.
At present, manufacturers requires while the size as far as possible reducing semi-conductor discrete device, reduce device forward voltage drop or conducting resistance, and this mainly relies on the resistivity reducing the polished section substrate manufacturing discrete device epitaxial wafer used to realize.Obtain the low polished section substrate of resistivity just to need to mix more phosphorus or the doping agent such as arsenic or antimony when growing adulterating vertical pulling silicon monocrystalline.
In order to obtain forward voltage drop or the conducting resistance of alap discrete device, current used N-type adulterating vertical pulling silicon monocrystalline is mainly resistivity and is less than the adulterated arsenic vertical gulling silicon monocrystalline of 0.003 Ω cm or 0.002 Ω cm (concentration of doping agent arsenic is greater than 2 × 10
19/ cm
3) and resistivity is less than the adulterated phosphorus vertical pulling silicon monocrystalline of 0.0015 Ω cm, and (concentration of doping agent phosphorus is greater than 4 × 10
19/ cm
3).Because doping content cannot continue to improve, (concentration range of doping agent antimony is 1 × 10 to reblended antimony czochralski silicon monocrystal
18/ cm
3-6 × 10
18/ cm
3) usage quantity very little.
Continue to improve the concentration (reducing the resistivity of silicon single-crystal) separately making the doped element in the N-type adulterating vertical pulling silicon monocrystalline of doping agent with phosphorus or arsenic and can encounter the problem that extension lattice mismatch becomes serious, the semiconductor device yield loss that the lattice mismatch of the epitaxial wafer processed by this czochralski silicon monocrystal causes can become and can not accept.
Summary of the invention
The object of this invention is to provide a kind of N-type adulterating vertical pulling silicon monocrystalline and silicon epitaxial wafer thereof of phosphorus arsenic antimony codoped.
A N-type adulterating vertical pulling silicon monocrystalline for phosphorus arsenic antimony codoped, phosphorus is as main doped element, and the one in arsenic, antimony or two kinds are as supplementary doping element, and the concentration of described phosphorus is more than or equal to 4.6 × 10
19/ cm
3, in doped element, accounting equals 60% greatly, and the accounting of supplementary doping element in doped element is 0.1%-40%.
The accounting 0.1%-40% in doped element of described supplementary doping element arsenic.
The accounting 0.1%-40% in doped element of described supplementary doping element antimony.
Described supplementary doping element arsenic and the antimony accounting sum in doped element is 0.1%-40%.
Adopt a silicon epitaxial wafer for the N-type adulterating vertical pulling silicon single crystal preparation of described phosphorus arsenic antimony codoped, the N-type adulterating vertical pulling silicon monocrystalline of described phosphorus arsenic antimony codoped is processed into polished section, then do substrate manufacture silicon epitaxial wafer by polished section.
A preparation method for the N-type adulterating vertical pulling silicon monocrystalline of described phosphorus arsenic antimony codoped, step is as follows:
1), unmelted polycrystalline silicon: first quartz crucible is loaded in straight pulling silicon single crystal furnace, then fill polysilicon in quartz crucible, vacuumize, be energized unmelted polycrystalline silicon, regulate power input to make silicon melt temperature-stable at 1460 ± 20 DEG C;
2), main doped element phosphorus is mixed: loaded by load weighted red phosphorus in quartz curette, again quartz curette is suspended in quartz bell cover, quartz bell cover is suspended on the seed chuck of monocrystal stove lift room, vacuumize, open the segregaion valve of lift bottom, room, position quartz bell cover being dropped to silicon melt surface 5-10mm in distance quartz crucible makes doping agent volatilize completely to be absorbed by silicon melt;
3), the mixing of arsenic and/or antimony: the method for mixing arsenic and/or antimony is identical with the method for mixing phosphorus;
4), single crystal growing: after completing the mixing of doped element, carry out the process of growth of silicon single-crystal according to common silicon monocrystal growth program, grow the N-type adulterating vertical pulling silicon monocrystalline of described phosphorus arsenic antimony codoped.
Beneficial effect of the present invention: the N-type adulterating vertical pulling silicon monocrystalline eliminating or significantly reduce the slip line caused because of lattice mismatch in silicon epitaxial wafer, the misfit dislocation L&S line defect produced when effectively can reduce or eliminate the polished section growing epitaxial layers processed at the N-type adulterating vertical pulling silicon monocrystalline by high-dopant concentration; And the problem that semiconducter device zone of transition broadens after pyroprocess can not be produced while this problem of solution; Changing multiple namely in silicon single-crystal in phosphorus arsenic antimony of industry practice can not simultaneously as doping agent.
Accompanying drawing explanation
Fig. 1 is in background technology, and after higher device temperature process, the resistivity of heavily doped arsenic substrate epitaxial sheet is in the distribution of depth direction.
Embodiment
Show the covalent radius contrast of silicon, phosphorus, arsenic, antimony in Table 1.
Table one is the contrast of silicon phosphorus arsenic antimony covalent radius
| Silicon | Phosphorus | Arsenic | Antimony | |
| The covalent radius () of atom | 1.11 | 1.06 | 1.2 | 1.4 |
Due to the difference of the covalent radius of atom in actual production, mix separately in high concentration phosphorus to silicon single-crystal and can cause Lattice Contraction, the lattice parameter of heavily doped phosphorus silicon single-crystal reduces relative to the silicon single-crystal that undopes; Contrary with phosphorus, mix separately in the arsenic of high density or antimony to silicon single-crystal and silicon crystal lattice can be caused to expand, the lattice parameter of heavily doped arsenic or heavy Sb-admixed silicon monocrystal increases relative to the silicon single-crystal that undopes.Because the resistivity of silicon epitaxy layer is all higher, corresponding doping agent is generally phosphorus and concentration is lower, is about 10
13-10
15/ cm
3the order of magnitude, when using the polished section of being processed by the N-type heavily-doped silicon mixing high concentration phosphorus, arsenic or antimony to make substrate growth epitaxial film, because the differences between lattice constant of silicon epitaxy layer and polished section substrate is too large, can lattice mismatch be produced, epitaxial film can be observed the line defect being called as misfit dislocation line.There is leakage current and the yield loss that misfit dislocation line can increase semiconducter device in epitaxial wafer.
The N-type adulterating vertical pulling silicon monocrystalline of phosphorus arsenic antimony codoped of the present invention mainly contains three types, and the first type is the N-type adulterating vertical pulling silicon monocrystalline grown as doping agent using phosphorus and arsenic two kinds of elements, and phosphorus is main doped element, and concentration is more than or equal to 4.6 × 10
19/ cm
3, in the doped element of czochralski silicon monocrystal, accounting is more than or equal to 60%, the accounting 0.1%-40% in doped element of supplementary doping element arsenic; The second type is that phosphorus is main doped element, and concentration is more than or equal to 4.6 × 10 with phosphorus and antimony two kinds of elements N-type adulterating vertical pulling silicon monocrystalline as doping agent
19/ cm
3, in the doped element of czochralski silicon monocrystal, accounting is more than or equal to 60%, the accounting 0.1%-40% of supplementary doping element antimony in doped element; The third is the N-type adulterating vertical pulling silicon monocrystalline using phosphorus, arsenic and antimony three kinds of elements as doping agent, and phosphorus is main doped element, and concentration is more than or equal to 4.6 × 10
19/ cm
3, in the doped element of czochralski silicon monocrystal, accounting is more than or equal to 60%, and supplementary doping element arsenic and the antimony accounting sum in doped element is 0.1%-40%.
The N-type adulterating vertical pulling silicon monocrystalline of phosphorus arsenic antimony codoped of the present invention, make use of in silicon crystal, the covalent radius of phosphorus atom is less than the covalent radius of Siliciumatom, the character that the covalent radius of arsenic and antimony atoms is larger than the covalent radius of Siliciumatom, utilize arsenic or antimony to compensate the volume effect of phosphorus (when using two kinds of element codopeds) or to utilize arsenic and antimony to compensate the volume effect of phosphorus (when using three kinds of element codopeds), the lattice parameter of the N-type adulterating vertical pulling silicon monocrystalline of high-dopant concentration is made to be reduced to permissible value relative to the change of the lattice parameter of intrinsic silicon monocrystalline, the dislocation line defect caused because of lattice mismatch produced when can eliminate or significantly reduce grown silicon epitaxial film in the polished section be processed into by such czochralski silicon monocrystal.Due to be using arsenic or antimony as supplementary doping element, using phosphorus as main doped element, the spread coefficient of phosphorus than arsenic and antimony large, adding of the arsenic of small amount and antimony can not the width of the extension zone of transition of remarkably influenced semiconducter device after pyroprocess, does not also affect significantly the voltage breakdown of the semiconducter device that following process becomes.
Table two is the spread coefficient contrast of phosphorus, arsenic, antimony in silicon, and the spread coefficient of phosphorus is maximum, and arsenic takes second place, and antimony is minimum.In adulterated arsenic vertical gulling silicon monocrystalline, be mixed into a small amount of phosphorus, in reblended antimony czochralski silicon monocrystal, be mixed into a small amount of phosphorus or arsenic can the width of the extension zone of transition of semiconducter device that is processed into by its epitaxial wafer of remarkably influenced.Because the spread coefficient of phosphorus is much larger than the spread coefficient of arsenic and antimony, when being mixed into a small amount of arsenic and antimony in adulterated phosphorus vertical pulling silicon monocrystalline, can not the width of the extension zone of transition of semiconducter device that is processed into by its epitaxial wafer of remarkably influenced, the voltage breakdown of semiconducter device namely can not be reduced because of the net thickness of epitaxial film after reducing device pyroprocess.Here " on a small quantity " refers to that the concentration of supplementary doping element is greater than 5 × 10
14/ cm
3and concentration is lower than main concentration of mixing element.The N-type adulterating vertical pulling silicon monocrystalline of a kind of phosphorus arsenic antimony codoped of the present invention and the silicon epitaxial wafer by its processing, the epitaxial film lattice mismatch issue produced when solving silicon polished substrate doping height, and solving the problem that can not to produce semiconducter device zone of transition after pyroprocess while this problem and broaden.
Table two
| Phosphorus | Arsenic | Antimony | |
| Spread coefficient cm when 1200 DEG C in silicon 2/s | 5×10 -12 | 2.5×10 -13 | 3.6×10 -13 |
The preparation method of the N-type adulterating vertical pulling silicon monocrystalline of described phosphorus arsenic antimony codoped, step is as follows:
1), unmelted polycrystalline silicon: first quartz crucible is loaded in straight pulling silicon single crystal furnace, then fill polysilicon in quartz crucible, vacuumize, be energized unmelted polycrystalline silicon, regulate power input to make silicon melt temperature-stable at 1460 ± 20 DEG C;
2), main doped element phosphorus is mixed: loaded by load weighted red phosphorus in quartz curette, again quartz curette is suspended in quartz bell cover, quartz bell cover is suspended on the seed chuck of monocrystal stove lift room, vacuumize, open the segregaion valve of lift bottom, room, position quartz bell cover being dropped to silicon melt surface 5-10mm in distance quartz crucible makes doping agent volatilize completely to be absorbed by silicon melt;
3), the mixing of arsenic and/or antimony: the method for mixing arsenic and/or antimony is identical with the method for mixing phosphorus;
4), single crystal growing: after completing the mixing of doped element, carry out the process of growth of silicon single-crystal according to common silicon monocrystal growth program, grow the N-type adulterating vertical pulling silicon monocrystalline of described phosphorus arsenic antimony codoped.
The N-type adulterating vertical pulling silicon monocrystalline of a kind of phosphorus arsenic antimony codoped of the present invention and the epitaxial film lattice mismatch issue produced when solving silicon polished substrate high-dopant concentration by the silicon epitaxial wafer of its processing, and the problem that can not produce that while solving this problem semiconducter device zone of transition after pyroprocess broadens.
Embodiment
Table three shows 5 specific exampless forming N-type adulterating vertical pulling silicon monocrystalline of the present invention, and the diameter of epitaxial wafer is 150mm.
Table three
| Example | Phosphorus (concentration, atom/cm 3） | Arsenic (concentration, atom/cm 3） | Antimony (concentration, atom/cm 3） | Epitaxy layer thickness (μ) | Epilayer resistance rate (Ω .cm) | Surface misfit dislocation (bar/sheet) |
| 1 | 7.3×10 19 | 0 | 0 | 20 | 6 | 120 |
| 2 | 7.1×10 19 | 2.2×10 18 | 0 | 20 | 6 | 16 |
| 3 | 7.0×10 19 | 0 | 2.8×10 18 | 20 | 6 | 5 |
| 4 | 4.9×10 19 | 2.6×10 19 | 0 | 20 | 6 | 0 |
| 5 | 5.3×10 19 | 1.3×10 19 | 1.1×10 19 | 20 | 6 | 0 |
From table three, except use phosphoric does except main doped element in N-type adulterating vertical pulling silicon monocrystalline, add the reduction of the silicon crystal lattice constant that phosphorus that antimony or arsenic energy effective compensation mix close concentration individually produces again, the misfit dislocation L&S line defect produced when significantly can reduce or eliminate grown silicon epitaxial film in the polished section using such czochralski silicon monocrystal to be processed into simultaneously.
Claims (6)
1. a N-type adulterating vertical pulling silicon monocrystalline for phosphorus arsenic antimony codoped, is characterized in that: phosphorus is as main doped element, and the one in arsenic, antimony or two kinds are as supplementary doping element, and the concentration of described phosphorus is more than or equal to 4.6 × 10
19/ cm
3, in doped element, accounting equals 60% greatly, and the accounting of supplementary doping element in doped element is 0.1%-40%.
2. the N-type adulterating vertical pulling silicon monocrystalline of phosphorus arsenic antimony codoped as claimed in claim 1, is characterized in that:
The accounting 0.1%-40% in doped element of described supplementary doping element arsenic.
3. the N-type adulterating vertical pulling silicon monocrystalline of phosphorus arsenic antimony codoped as claimed in claim 1, is characterized in that:
The accounting 0.1%-40% in doped element of described supplementary doping element antimony.
4. the N-type adulterating vertical pulling silicon monocrystalline of phosphorus arsenic antimony codoped as claimed in claim 1, is characterized in that:
Described supplementary doping element arsenic and the antimony accounting sum in doped element is 0.1%-40%.
5. one kind adopts the silicon epitaxial wafer of the N-type adulterating vertical pulling silicon single crystal preparation of the phosphorus arsenic antimony codoped as described in any one of claim 1-4, it is characterized in that: the N-type adulterating vertical pulling silicon monocrystalline of described phosphorus arsenic antimony codoped is processed into polished section, then do substrate manufacture silicon epitaxial wafer by polished section.
6. a preparation method for the N-type adulterating vertical pulling silicon monocrystalline of the phosphorus arsenic antimony codoped as described in any one of claim 1-4, is characterized in that: step is as follows:
1), unmelted polycrystalline silicon: first quartz crucible is loaded in straight pulling silicon single crystal furnace, then fill polysilicon in quartz crucible, vacuumize, be energized unmelted polycrystalline silicon, regulate power input to make silicon melt temperature-stable at 1460 ± 20 DEG C;
2), main doped element phosphorus is mixed: loaded by load weighted red phosphorus in quartz curette, again quartz curette is suspended in quartz bell cover, quartz bell cover is suspended on the seed chuck of monocrystal stove lift room, vacuumize, open the segregaion valve of lift bottom, room, position quartz bell cover being dropped to silicon melt surface 5-10mm in distance quartz crucible makes doping agent volatilize completely to be absorbed by silicon melt;
3), the mixing of arsenic and/or antimony: the method for mixing arsenic and/or antimony is identical with the method for mixing phosphorus;
4), single crystal growing: after completing the mixing of doped element, carry out the process of growth of silicon single-crystal according to common silicon monocrystal growth program, grow the N-type adulterating vertical pulling silicon monocrystalline of described phosphorus arsenic antimony codoped.
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| CN112713219A (en) * | 2020-12-29 | 2021-04-27 | 上海微波技术研究所（中国电子科技集团公司第五十研究所） | Co-doped blocking impurity band detection system and method |
| CN114381799A (en) * | 2021-12-31 | 2022-04-22 | 杭州中欣晶圆半导体股份有限公司 | Method for eliminating heavily antimony-doped pipeline |
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| CN104711675B (en) | 2017-11-10 |
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