CN1003797B - Preparation method of micronitrogen,low-oxygen, low-carbon, vertical pull monocrystalline silicon - Google Patents
Preparation method of micronitrogen,low-oxygen, low-carbon, vertical pull monocrystalline silicon Download PDFInfo
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- CN1003797B CN1003797B CN88100307.7A CN88100307A CN1003797B CN 1003797 B CN1003797 B CN 1003797B CN 88100307 A CN88100307 A CN 88100307A CN 1003797 B CN1003797 B CN 1003797B
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Abstract
The present invention relates to a preparation method for a vertical-pulling silicon monocrystalline with micro nitrogen, low oxygen and low carbon. In the preparation method, a monocrystalline furnace with an external magnetic field is used. The vertical-pulling silicon monocrystalline with micro nitrogen, low oxygen and low carbon is prepared by using nitrogen gas of which the purity is 99.99% or argon-nitrogen mixed gas as protective gas and executing the reasonable control of pressure in the furnace and the flow rate of gas and other technologies. The produced vertical-pulling silicon monocrystalline with micro nitrogen, low oxygen and low carbon has oxygen content lower than 10 ppma, carbon content lower than 1 ppma and doped nitrogen content lower than 4.5*10<15> per cubic centimeter.
Description
The invention belongs to the silicon monocrystal growth technology, relate in particular to nitrogen, oxygen, carbon content control techniques in the czochralski silicon monocrystal.
At present, the CZ-silicon single-crystal that large-scale integrated circuit is commonly used, its major impurity is oxygen and carbon.Oxygen, the carbon impurity behavior more complicated in silicon it is generally acknowledged that the effect of oxygen is both advantageous and disadvantageous, and carbon is then only harmful and unhelpful.When carbon content surpasses 5 * 10
16Cm
-3The time, the performance degradation of semiconducter device, the reverse characteristic deliquescing, voltage breakdown descends; Carbon content is high more, and the yield rate of device is low more.
Developing rapidly because LSI/VLSI(large-scale integrated circuit/super large-scale integration), people are more and more higher to the requirement of silicon single-crystal quality, and especially the uniform distribution to impurity oxygen in the silicon single-crystal requires more strict.The silicon single-crystal of vertical pulling prepared (CZ-Si) contains a considerable amount of oxygen (～10
16Cm
-3), because oxygen has pinning effect to dislocation in the silicon, the oxygen of certain content helps improving the physical strength of silicon chip, prevents silicon chip warpage and fragmentation in device technology.But when oxygen level is higher among the CZ-Si, then produce a lot of drawbacks, such as hot alms giver, new alms giver, oxygen precipitation and various microdefects etc.People attempt to adopt silicon single-crystal (FZ-Si) the replaced C Z-Si of the molten suspension process preparation in district, and are then low by (～10 because of oxygen level
16Cm
-3), have higher electronic mobility and its superiority is arranged.But the FZ-Si silicon chip can't overcome and caused by low oxygen content to produce warpage and disruptive shortcoming in the device technology process.In view of oxygen this dual function in silicon, make vast semiconducter device worker propose, to different device technologies, should adopt the silicon chip of different oxygen, and wish vertical and section oxygen level uniform distribution in the silicon single-crystal.Therefore the control problem of oxygen in the silicon single-crystal (CZ-Si) of vertical pulling prepared has become since the eighties very noticeable important topic in the silicon monocrystal growth technology.Czochralski silicon monocrystal in the magnetic field (MCZ) technology is being arisen at the historic moment in the background like this, and the MCZ method that deliver in May, 1980 in the 15th ECS of the U.S. has caused the great repercussion of people.
After in the CZ method, having added magnetic field, the electric conductivity object that thermal convection produced of silicon melt, motion in magnetic field is subjected to new reactive force, suppressed thermal convection, thereby controlled the speed that near the quartz crucible wall oxygen is transported to the growth solid-liquid interface, greatly reduce the oxygen level in the czochralski silicon monocrystal (CZ-Si), make oxygen level be lower than 1 * 10
17Cm
-3(2ppma).Owing to suppress the melt thermal convection, also suppressed the generation of microdefect and impurity striation simultaneously.Yet the MCZ silicon single-crystal of low oxygen content is similar to the FZ-Si silicon single-crystal like this, can't overcome silicon chip because yielding stress reduces and easily produce shortcomings such as warpage in the device technology process.Along with the ever-larger diameters of silicon single-crystal, diameter is greater than 4, and " this gentle shield of silicon single-crystal is especially outstanding.Add that the MCZ-Si power consumption has increased by two times, so MCZ-Si fails commercialization and become the material that is useful for super large-scale integration (VLSI) so far.
People seek the silicon single-crystal of a kind of hypoxemia, low carbon high-strength degree with dreaming of for many years, to satisfy the needs of growing VLSI technology.
People (Semiconductor silicon1981 p54) such as the Ah portion of Japan XINYUE filial piety husband propose to mix the physical strength that nitrogen can improve silicon chip in the FZ-Si silicon single-crystal, but for diameter greater than 3 " the suitable difficulty of FZ-Si single crystal preparation.So people (VLSI Sciencend Technology 1985P543) such as Ah filial piety husband propose again to add Si in molten silicon
3N
4Powder is produced the nitrating czochralski silicon monocrystal, improving the mechanical property of silicon single-crystal, because technology is difficult to grasp, fails to be applied to industrial production so far.
Application number has proposed the gas phase nitrogen-doping method of czochralski silicon monocrystal for the CN87105811 patent, can improve the physical strength of large-diameter silicon wafer, further suppress microdefect in the silicon single-crystal, but because nitrogen, oxygen and the behavior of carbon in silicon are more complicated, mutual restriction, the content of rationally controlling oxygen in the silicon, carbon and nitrogen is still very urgent task.And being the CN87105811 patent, application number do not relate to this respect problem.
Task of the present invention is to provide a kind of preparation method of silicon single-crystal of little nitrogen hypoxemia low-carbon (LC) of suitable VLSI needs.
Present method is under the czochralski silicon monocrystal processing condition of routine, comprise that externally-applied magnetic field is 1000～5000 Gausses, crucible rotation is 5～20 rev/mins, the polycrystalline charging capacity is 20～60 kilograms in the crucible, the crystal rotating speed is 10～30 rev/mins, pulling rate is 0.8～1.5 millimeter/minute, adopts following measure to prepare diameter 2 "～6 ", is fit to little nitrogen, hypoxemia, the low-carbon (LC) czochralski silicon monocrystal of LSI/VLSI demand.
In order to reduce oxygen level in the silicon,, make molten silicon and SiO at surperficial coated one deck silicon nitride film of quartz crucible
2Isolated; Under externally-applied magnetic field, suitably adjust seed crystal rotating speed, crucible rotation and pulling rate simultaneously, three's cooperation just can be controlled the oxygen level in the silicon single-crystal effectively, and oxygen level is reached below the 10ppma.Oxygen level is less than the silicon chip of 10ppma, and its physical strength is affected, for diameter greater than 4 " the CZ-Si monocrystalline especially obvious.Mix trace nitrogen.Then this influence can be eliminated,, the mechanical property of low oxygen concentration silicon chip can be improved significantly because nitrogen is stronger than oxygen to the pinning effect of dislocation.
Apply magnetic field and neglect charging capacity greatly and decide for suppressing thermal convection in the silicon melt, charging capacity is big more, and the magnetic field that applies is also big more.Added magnetic field can be linear magnetic field, or non-linear magnetic field, or cryogenic magnetic field etc.
The present invention adopts nitrogen more than 99.99% or argon-nitrogen mixed gas as shielding gas, and furnace pressure is 5～80 holders, and gas flow is 4～16 meters
3/ hour, the furnace pressure optimum value is 15～25 holders.
For controlling the content of carbon and nitrogen in the silicon single-crystal effectively, according to the size of silicon single-crystal diameter, adopt different flow parameters, diameter is big more, and flow is also big more.The preparation diameter be 3 " silicon single-crystal the time, the gas optimum flow is 4～6 meters
3/ hour; The preparation diameter be 4 " silicon single-crystal the time, the gas optimum flow is 5～8 meters
3/ hour; The preparation diameter be 5 " during silicon single-crystal, the gas optimum flow is 7～10 meters
3/ hour; The preparation diameter be 6 " silicon single-crystal the time, the gas optimum flow is 9～12 meters
3/ hour;
Adopt argon-nitrogen mixed gas as shielding gas, wherein the argon gas composition is 2～10%, and the nitrogen composition is 98～90%, according to the requirement of mixing nitrogen content is selected for use.
Adopt the air-flow of big flow to avoid the contamination of obnoxious flavoures such as carbon monoxide to protect molten silicon face and crystal.
In the prepared little nitrogen hypoxemia low-carbon (LC) czochralski silicon monocrystal of present method, oxygen level can be lower than 10ppma, and carbon content can be lower than 1ppma, and nitrogen concentration can be lower than 4.5 * 10
15Atom/cm
2Because prepared silicon single-crystal diameter, resistivity, oxygen and carbon content etc. are required difference, and the nitrogen content that is mixed has nothing in common with each other, require little crystal for the longitudinal resistivity uniformity coefficient, can make gas flow increase gradually.
Technology of the present invention also applicable to the preparation diameter greater than 6 " silicon single-crystal.
Present technique relatively has following advantage with existing C Z-Si, MCZ-Si technology:
1, adopt purity be 99.99% nitrogen or argon-nitrogen mixed gas as shielding gas, can reduce the production cost of silicon single-crystal significantly.
2, improve the over-all properties of silicon single-crystal, particularly improve the physical strength of large-diameter silicon wafer effectively, the yield rate of device is improved, high-grade product ratio increases.
3, the prepared little nitrogen hypoxemia low-carbon (LC) czochralski silicon monocrystal of present method is a kind of ideal material of making large-scale integrated circuit and super large-scale integration, helps quickening to realize the ever-larger diameters of silicon single-crystal simultaneously.
Embodiment 1:
Adopt the crystal growth parameter of known technology, draw on the monocrystal stove at the less energy-consumption magnetic that adds 1000～5000 Gausses, the quartz crucible diameter is 305 millimeters of φ; the policrystalline silicon charging capacity is 20 kilograms; adopt 99.99% purity nitrogen as shielding gas, furnace inner gas pressure is 10 holders, and gas flow is 4.5 meters
3/ hour, 20 rev/mins of brilliant commentaries on classics, crucible changes 8 rev/mins, and pulling rate is 1.5 millimeters/minute, obtains nitrogenous 7 * 10
14Atom/cm
3, oxygen level is less than 10ppma, carbon content 4 " silicon single-crystal 14.1kg less than 1ppma.
Embodiment 2
Adopt argon-nitrogen mixture gas as shielding gas, wherein the argon gas composition is 5%, and the nitrogen composition is 95%, and remainder data is identical with embodiment 1.
Embodiment 3～20 is similar to embodiment 1 or 2, and its difference is represented by table 1.
Claims (7)
1, a kind of preparation method of little nitrogen hypoxemia low-carbon (LC) czochralski silicon monocrystal, comprise that externally-applied magnetic field is 1000～5000 Gausses, crucible rotation is 5～20 rev/mins, the polycrystalline charging capacity is 20～60 kilograms in the crucible, and the crystal rotating speed is 10～30 rev/mins, and pulling rate is 0.8～1.5 millimeter/minute, crystal diameter is 2 "～6 ", it is characterized in that: adopt nitrogen or 99.99% above argon-nitrogen mixed gas more than 99.99% that silicon is made gas phase nitrogen-doping, furnace inner gas pressure is 5～80 holders, and gas flow is 4～16 meters
3/ hour.
2, the preparation method of silicon single-crystal according to claim 1 is characterized in that: the optimum value of furnace inner gas pressure is 15～25 holders.
3, the preparation method of silicon single-crystal according to claim 1 is characterized in that: to draw diameter be 3, and " during silicon single-crystal, gas flow is 4～6 meters
3/ hour.
4, the preparation method of silicon single-crystal according to claim 1 is characterized in that: to draw diameter be 4, and " during silicon single-crystal, gas flow is 5～8 meters
3/ hour.
5, the preparation method of silicon single-crystal according to claim 1 is characterized in that: to draw diameter be 5, and " during silicon single-crystal, gas flow is 7～10 meters
3/ hour.
6, the preparation method of silicon single-crystal according to claim 1 is characterized in that: to draw diameter be 6, and " during silicon single-crystal, gas flow is 9～12 meters
3/ hour.
7, the preparation method of silicon single-crystal according to claim 1 is characterized in that: adopt argon-nitrogen mixed gas as nitrating gas, wherein the argon gas composition is 2～10%, and the nitrogen composition is 98～90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88100307.7A CN1003797B (en) | 1988-01-20 | 1988-01-20 | Preparation method of micronitrogen,low-oxygen, low-carbon, vertical pull monocrystalline silicon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88100307.7A CN1003797B (en) | 1988-01-20 | 1988-01-20 | Preparation method of micronitrogen,low-oxygen, low-carbon, vertical pull monocrystalline silicon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN88100307A CN88100307A (en) | 1988-07-27 |
| CN1003797B true CN1003797B (en) | 1989-04-05 |
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ID=4831286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88100307.7A Expired CN1003797B (en) | 1988-01-20 | 1988-01-20 | Preparation method of micronitrogen,low-oxygen, low-carbon, vertical pull monocrystalline silicon |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851779A (en) * | 2010-06-04 | 2010-10-06 | 浙江芯能光伏科技有限公司 | Method for manufacturing monocrystalline silicon chip of solar cell |
| CN102409401B (en) * | 2010-09-26 | 2014-07-23 | 江国庆 | Technology for removing impurities by utilizing nitrogen-argon mixed gas in process of growing single crystal silicon by Czochralski method |
| CN104357901A (en) * | 2014-10-30 | 2015-02-18 | 内蒙古中环光伏材料有限公司 | Method for reducing oxygen donor content of Czochralski monocrystal |
| CN108138354B (en) * | 2015-05-01 | 2021-05-28 | 各星有限公司 | Method for producing single crystal ingot doped with volatile dopant |
| JP6090391B2 (en) * | 2015-08-21 | 2017-03-08 | 株式会社Sumco | Method for producing silicon single crystal |
-
1988
- 1988-01-20 CN CN88100307.7A patent/CN1003797B/en not_active Expired
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|---|---|
| CN88100307A (en) | 1988-07-27 |
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