WO1986003523A1 - Barres de silicium monocristallin a tirage en continu - Google Patents
Barres de silicium monocristallin a tirage en continu Download PDFInfo
- Publication number
- WO1986003523A1 WO1986003523A1 PCT/US1984/001980 US8401980W WO8603523A1 WO 1986003523 A1 WO1986003523 A1 WO 1986003523A1 US 8401980 W US8401980 W US 8401980W WO 8603523 A1 WO8603523 A1 WO 8603523A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silicon
- particles
- single crystal
- molten body
- ingot
- Prior art date
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 134
- 239000010703 silicon Substances 0.000 claims abstract description 134
- 239000013078 crystal Substances 0.000 claims abstract description 74
- 239000002019 doping agent Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims description 61
- 239000004065 semiconductor Substances 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 30
- 239000011856 silicon-based particle Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010924 continuous production Methods 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000000155 melt Substances 0.000 description 25
- 239000012535 impurity Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 19
- 239000012530 fluid Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- VQPFDLRNOCQMSN-UHFFFAOYSA-N bromosilane Chemical class Br[SiH3] VQPFDLRNOCQMSN-UHFFFAOYSA-N 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 4
- 238000010923 batch production Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- -1 phophorous Chemical compound 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical group Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IBOKZQNMFSHYNQ-UHFFFAOYSA-N tribromosilane Chemical compound Br[SiH](Br)Br IBOKZQNMFSHYNQ-UHFFFAOYSA-N 0.000 description 2
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011330 nucleic acid test Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C30B15/002—Continuous growth
-
- 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
Definitions
- Zisld ⁇ l ⁇ hs invention This invention relates to semiconductor grade silicon and, more particularly, to a method of producing large single crystal doped silicon ingots on a continuous basis.
- Semiconductor grade silicon is a foundational to the large and growing semiconductor, computer, instrumentation and electronic industries.
- Semi ⁇ conductor grade silicon is characterized by the requirement of ultrahigh purity, a level of purity not required and largely unattainable in other fields of chemical and metallurgical technology.
- Another char- acteristic of semiconductor grade silicon is the requirement, in some applications, that the silicon contain minute but precisely known or controlled amounts of specific impurities. This is known as "doping" silicon and the product is referred to as “doped" silicon.
- Exemplary of the elements with which silicon is doped are boron, phophorous, arsenic and antimony.
- Boron is ⁇ typical "electron acceptor” and phosphorous is a typical "electron donor”.
- the semiconductor industry is well developed now and there are thousands of semiconductor devices marketed directly or assembled into computers, radios, televisions, controllers and nearly an infinite variety of other electronic devices.
- Single crystal silicon ingots are produced using a very well-known and widely used classical technique for growing single crystals known as the Czhrochalski method, sometimes referred to as the CZ method.
- Single crystal ingots of metals are grown according to the Czchrochalski method by contacting a small single crystal of the metal to be grown with a molten body of the metal and drawing the single crystal away from the molten body of metal slowly while rotating the single crystal.
- the single crystal is kept at a temperature lower than the melting point of the crystal.
- the layer of molten metal adjacent the crystal in immediate contact with the crystal, only a few atoms thick, deposits on the single crystal seed and the seed grows.
- the atoms of the molten metal deposit in the same crystal structure as the seed and, thus, a larger single crystal is formed. This process continues with layer upon layer of single crystal being deposited upon the growing ingot until a large ingot is formed. These ingots may be very large, weighing upward of 100 kg typically and may be several inches in diameter and a few feet in length. If the seed and the molten metal are of high purity metal, such as semiconductor silicon in the present context, then the result is a single crystal of ultrahigh purity semiconductor grade silicon in which the crystal structure is virtually perfect. A number of adaptations and variations for growing single crystals are known, see, for example, U.S. Patents Nos. 3,998,598, 4,282,184, 4,410,494, 4,454,096 and 4,458,152.
- the Czhrochalski method is not without limitations, however, and while the production of perfect ultrahigh purity silicon is one of technology's crowning achievements, the method is subject to serious problems.
- the Czhrochalski method is generally performed as a batch process. A given quantity of silicon from any convenient source is melted in a crucible and drawn on a seed crystal until the molten metal is depleted. If the silicon feedstock were perfectly pure, and if there were no impurities introduced in the process, then a perfect single crystal of perfectly uniform purity could, in theory, be produced. Such is not possible, however, and the presence of even minute impurities creates non- uniformity in the ingot purity.
- partitioning occurs wherein the impurities preferentially migrate into the crystal being grown or remain preferentially in the melt — the latter being more common.
- the partitioning effect favors build up of impurities in the melt.
- the concentration cf impurities in the molt increases. Since the partition effect results in a relatively constant percentage of the impurity present in the mel being partitioned into the crystal, as the level of impurity in the melt increases during growth of the crystal, the level of the impurity in the crystal also increases. Thus, the impurity level in the crystal increases as the crystal is grown. (The converse would occur if the impurities partitioned preferentially int
- a principle feature of the present invention is a method of growing single crystal silicon ingots b a modified Czhrochalski process on a continuous or sem continuous basis wherein the ingots have a uniform level of dopant along the length of the ingot.
- the material is • difficult to handle and cannot be fed into a crucible in a precisely metered manner.
- the act of providing, or attempting to provide, a continuous feed tends to disturb the CZ furnace heat balance and stability thus causing or increasing the risk of a defective crystal growth.
- the silicon is crushed into fine powder, it acquires an enormous surface area and acquires substantial impurities simply from the crushing [ ⁇ ration. With the large, irregular surface area of such a product, it is virtually impossible to feed silicon in crushed or comminuted form into a furnace without introducing large amounts of oxygen and other adsorbed and absorbed impurities into the melt. Product quality always suffers and the risk of large numbers of very expensive rejected ingots is significantly increased.
- An important feature of the present invention is that it solves all or most of the problem of the prior art respecting continuous growth of silicon ingots and thus opens the way for the economic production of extremely high quality, ultrahigh purity, perfect single crystal silicon ingots on a substantially continuous basis.
- the present invention may be de cribed as a method for continuously producing semiconductor grade silicon by (a) producing spherical, low surface to volume ratio, nonagglomerated individual monodisperse particles of silicon having a diameter of from about 1/2 to about 2 mm, (b) forming a molten body of silicon, (c) continuously feeding the monodisperse particles of silicon of step (a) into the molten body of step (b) , and (d) drawing a single crystal of silicon continuously from the molten body of silicon o step (b) to thereby form an ingot of ultrahigh purity silicon having substantial uniform composition along the entire length of the ingot.
- the present invention is most advantageous as a 8 method for continuously producing an ingot of silicon having a constant leval of doping along the length thereof by (a) forming a body of molten silicon, (b) continuously feeding into said molten body ultrahigh purity spherical, low surface to volume ratio, nonagglomerated individual monodisperse particles of silicon having a diameter of from about 1/2 to about 2 mm, ( ⁇ ) producing spherical, low surface to volume ratio, nonagglomerated individual monodisperse particles of silicon containing a predetermined quantity of dopant and having a diameter of from about 1/2 to about 2 mm, (d) continuously feeding into said molten body the particles of step ( ⁇ ), and (e) continuously drawing a single crystal of silicon having a constant level of dopant from the molten body of dopant containing silicon to thereby produce an ingot of semiconductor grade silicon 'having a.uniform concentration of dopant therein along the length of the ingot.
- the present invention may also be described as a method of producing on a continuous basis doped silicon ingots having constant composition along the length thereof, comprising feeding two streams of spherical, low surface to volume ratio, nonagglomerated individual monodisperse particles of silicon into a molten body of silicon, one of said streams being of higher purity than the other stream, the other stream comprising silicon containing dopant, and continuously pulling a single crystal from the molten body.
- the present invention encompasses the very important and unexpected discovery of a unique form of silicon, and singularly striking and unobvious use of such silicon in a new method for producing perfect single crystal silicon ingots on a continuous basis.
- silicon can be produced in the form of spherical, low surface to volume ratio, nonagglomerated individual monodisperse particles of silicon having a diameter of about 1 mm average with a maximum size distribution from about 1/2 to about 2 mm in diameter.
- This product is a free flowing "shot-like" product with each sphere being very nearly perfect, and approximately the same size as every other sphere.
- Semiconductor grade as used here is as defined in the semiconductor device fabrication industry, e.g., 0.1 ppb boron, 0.3 ppb phosphorus, etc.
- This feedstock is formed by thermal decomposition or hydrogen reduction of bromosilanes at 600°C to 1000°C at about atmospheric pressure in a "fluidized bed" reactor to achieve a product diameter from 1/2 millimeter to 2 millimeters.
- Suitable substrate particles for feedstock to the fluid bed reactor can be created by crushing or attrition of larger particles, The form of the small substrate particles is unimportant - only their purity and freedom from contamination.
- the spherodicity of the product of Step 1 of the Schumacher Silicon Process is developed during deposition onto these "substrate” particles fed into the Step 1 fluid bed reactor.
- the deposition results of course from the thermal decomposition or hydrogen reduction of the bromosilane compound to produce silicon and various by-products depending on the exact bromosilane and decomposition reduction method chosen.
- Sintering avoidance is accomplished in the bromosilane system by its low decomposition temperature, being lowest for thermal decomposition, and raised by hydrogen dilution as a result of some hydrogen reduction, e.g.
- T_ being higher than T-, .
- Sintering is a result of surface diffusion under the driving force of surface curvature which causes a distribution of particles to eliminate --..iriall particles and grow large particles, reducing the overall, net surface to volume ratio, and binds together the particles in contact with one another to again reduce the system surface/volume ratio.
- Step 1 reactor is a fluid bed reactor
- contact times between particles are of a short duration, so that sintering does not become a problem until somewhat higher temperatures, at about 1000°C - 1050°C due to this and the monodisperse character of the product.
- Step 2 doped silicon is produced for addition of donors and acceptors to the continuous CZ melt.
- Step 2 operates identically to Step 1, except that the bromosilane working fluid employed in the process is not as pure as possible, but is taken from that part of the process where donors or acceptors are concentrated.
- Make-up working fluid and BBr- ⁇ ) or PBr z,> are added to the feed streams to cause sufficient boron or phosphorus doped polycrystalline silicon of extremely low metals content (semiconductor grade) to be produced in a fluid bed reactor designated for this purpose.
- Step 3 of the SSP is the continuous or semicontinuous production of constant composition single crystal silicon lvia the CZ process of seed withdrawal from the melt.
- current technology which employs batch melting of a specific quantity (5-10 up to 60 or 100 or more kg) of semiconductor grade polycrystalline silicon produced via the Siemen's Process, or a fluid bed process which does not utilize bromosilane chemistry and is, therefore, incapable of producing continuous CZ feedstock from Steps 1 and 2, a partioning of impurities occurs across the solid-liquid phase boundary, since impurities, including donors and acceptors, exist in different equilibrium concentrations in a liquid in equilibrium with its solid phase.
- concentration -of impurities vary with time in the melt and, therefore, with position in the solid solidified from that melt.
- An important feature of the present invention is the step of adding a controlled number of spherical, low surface to volume ratio, nonagglomerated individual monodisperse particles of silicon having a mean diameter of about 1 mm to the silicon melt at a constant rate, typically sphere-by-sphere to subtantially exactly replenish the melt as the single crystal grows, but without disrupting or disturbing the mass or thermal balance and stability of the crucible or melt. Since the
- solid feedstock is introduced in particles characterized as spherical, thus having the minimum possible surface to volume ratio, and being nonagglomerated individual monodisperse particles of silicon having an approximately uniform diameter of about 1 mm, the effect on the mass of the melt, and upon the heat balance, i.e., the heat required to melt the added silicon and compensate for losses to the single crystal and to the environment, is a function of the rate of introduction of the individual particles. Since the rate of introduction of individual particles, one or more at a time, of substantially identical heat capacity can be controlled and kept constant, there are no disturbances or "spikes" in the heat absorbed in the system or required of the heating source. It is difficult to overestimate the importance of this facet of the invention, as it makes possible the .very reliable growth of perfect single crystal silicon on a continuous basis.
- Melt composition is maintained essentially constant with respect to the desired constituent of the product ingot doping with additions of SSP using Step 2 product as feedstock.
- the Schumacher Silicon Process comprises the following steps to produce a superior quality wafer for semiconductor device manufacturing, including integrated circuits and silicon photovoltaic solar cells.
- This uniformity is developed by the continuous, or semi-continuous, pulling of CZ crystal from a melt in which constant thermal gradients and constant constitutional gradients exist, and only build up of minor constituents takes place. About 300 ft. of crystal can be pulled prior to too much build up of minor constituents.
- additions to the melt must, in fact, melt prior to coming into contact with the growing solid-liquid interface, so that additions are made behind a weir or other arrangements to provide sufficient time for such additions to melt, prior to being brought by convection to the region of the growing solid-liquid interface.
- the weir arrangement is the only feature distinguishing the SSP crucible from ordinary CZ
- Crystal may be pulled from a shallow melt, or a deep melt.
- Various forms of heating, inductive, resistance, R F, microwave, etc. may be used.
- Electromagnetic fields to control wall contact and melt convection paths may be employed. All of these are known in the art of CZ pulling of single crystal silicon of semiconductor grade.
- the apparatus in which SSP is operated differs from the standard crystal pull furnace only in that arrangement made for handling of the ingot as it is withdrawn from the melt.
- the standard tower will handle only a limited length ingot.
- an arrangement is made to keep the crystal aligned to within .the critical angle with the melt by side supports which also serve to support the load, at least partially.
- the product ingot is then much longer than typical ingots, and.has a much reduced variation with position of both minor and major solute species than conventional CZ ingots.
- This ingot is then sliced, lapped, and polished into wafers by conventional means. These wafers show little variation in doping, defects, or impurity concentration from one wafer to the next, and from one end of the ingot to the other, clearly a vast improvement in the state of the art.
- Example 1 Ultrahigh purity monodisperse spherical particles of silicon were manufactured according to the process described in U.S. Patent No. 4,084,942.
- the particles are of high density, of nearly uniform size, from 1/2 to 2 mm and principally about 1 mm in diameter, and formed a free flowing product which was free of fines and dust.
- a controlled concentration of dopant e.g., boron tribromide or phosphorous tribromide
- the dopant concentration may be at any desired and effective level, generally in the range from 0.001 to 1 ppm, as this product will be used as feedstock to the silicon melt to contribute a low level of dopant.
- Higher dopant concentrations may be used as well, since any ratio of feedstocks can be used to control the dopant concentration in the silicon melt.
- a body of molten silicon is made up of the desired ratio of feedstocks from the proceeding steps, namely ultrahigh purity silicon and doped silicon, to form a melt of uniform composition.
- the composition is maintained uniform during the. entire operation of the process by continuously feeding in the ratio of feedstocks required.
- a melt having 5 ppb dopant is maintained by feeding equal quantities of ultrahigh purity silicon, less than 0.1 ppb, and doped silicon having 10 ppb dopant.
- a single crystal of silicon, which- may be of ultrahigh purity is contacted into the melt and withdrawn while being rotated, according to the classical Czhrochalski technique, thus growing a single crystal ingot having a uniform composition along the entire length of 5 ppb.
- the single crystal may be drawn continuously from the melt for very long periods of time. Calculations indicated that a single crystal up to 300 feet long is entirely feasible, although equipment design and handling convenience suggest that a crystal of this long may not be efficiently handled.
- the method of this invention comprises producing single crystal ingots continuously by forming a molten body of silicon metal of two feedstocks of silicon, one feedstock containing a predetermined level of dopant; continuously drawing a single crystal ingot of doped silicon from said molten body of silicon, said ingot being
- the concentration of dopant is uniform along the length of the ingot, while continuously feeding said feedstocks into said molten body of silicon to thereby maintain the concentration of dopant uniform in said body during the drawing of the single crystal therefrom.
- continuous, or continuously, as used herein means carrying out the process while repeating the steps set forth either periodically, or without interruption.
- a continuous process sometimes referred to as semi-co tinuous, would involve the repeated periodic introduction of silicon material feedstock while the crystal was being drawn from the melt, as well as constantly adding silicon material feedstock during drawing of every feedstock. Every feedstock inherently contains some impurity or additive, hence, the terms ultrapure silicon and doped silicon are used in the normal technical meaning of these terms.
- the two feedstocks could, within the scope of the invention, contain, respectively, two concentrations of the same dopant or concentrations, the same or different, of two or more dopants.
- the method of the invention may be described as including the steps of feeding a first feedstock into a molten body of silicon metal, said first feedstock comprising ultrahigh purity semiconductor grade silicon; feeding a second feedstock comprising ultrahigh purity semiconductor grade silicon to which a known amount of semiconductor dopant has been added; and, while carrying out the above-stated steps, drawing a single crystal of doped silicon from said molten body.
- the method of the invention preferably includes the steps of introducing into said molten body a first silicon composition characterized in being spherical, low surface to volume ratio, nonagglomerated individual, monodisperse silicon particles having a diameter of about 1 mm, and introducing into said molten body a second silicon composition characterized in being spherical, low surface to volume
- the doped silicon particles preferably contain boron, antimony, arsonic, or phosphorous.
- the silicon particles and the doped silicon particles have a mean diameter of about 1 mm, and the particle feedstocks are substantially free of sintered particles, particles substantially over 2 mm in diameter, and fine particles substantially under 1/2 mm in diameter.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Procédé de production en continu de barres de silicium monocristallin consistant à former un corps en fusion de silicium métal à partir de deux charges de silicium dont l'une contient un degré prédéterminé de dopant, à tirer en continu une barre de silicium dopé monocristallin à partir dudit corps de silicium en fusion, ladite barre étant caractérisée en ce que la concentration de dopant est uniforme sur toute la longueur, tout en introduisant en continu lesdites charges dans ledit corps de silicium en fusion pour ainsi y maintenir uniforme la concentration de dopant durant le tirage du monocristal.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19850900367 EP0205422A4 (fr) | 1984-12-04 | 1984-12-04 | Barres de silicium monocristallin a tirage en continu. |
PCT/US1984/001980 WO1986003523A1 (fr) | 1984-12-04 | 1984-12-04 | Barres de silicium monocristallin a tirage en continu |
JP60500119A JPS62501497A (ja) | 1984-12-04 | 1984-12-04 | 連続して引き出される単結晶シリコンインゴット |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1984/001980 WO1986003523A1 (fr) | 1984-12-04 | 1984-12-04 | Barres de silicium monocristallin a tirage en continu |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1986003523A1 true WO1986003523A1 (fr) | 1986-06-19 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1984/001980 WO1986003523A1 (fr) | 1984-12-04 | 1984-12-04 | Barres de silicium monocristallin a tirage en continu |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0205422A4 (fr) |
JP (1) | JPS62501497A (fr) |
WO (1) | WO1986003523A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5126114A (en) * | 1987-12-08 | 1992-06-30 | Nkk Corporation | Manufacturing method and equipment of single silicon crystal |
EP0494312A4 (en) * | 1990-07-26 | 1993-01-20 | Sumitomo Electric Industries, Ltd. | Method and apparatus for making single crystal |
DE10250822A1 (de) * | 2002-10-31 | 2004-05-19 | Wacker Siltronic Ag | Verfahren zur Herstellung eines mit leichtflüchtigem Fremdstoff dotierten Einkristalls aus Silicium |
EP1577954A1 (fr) * | 2004-03-09 | 2005-09-21 | RWE SCHOTT Solar GmbH | procédé de transport des particules solides |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9664448B2 (en) * | 2012-07-30 | 2017-05-30 | Solar World Industries America Inc. | Melting apparatus |
CN109972200B (zh) * | 2019-04-18 | 2020-08-14 | 邢台晶龙电子材料有限公司 | 连续提拉单晶硅生长方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4036595A (en) * | 1975-11-06 | 1977-07-19 | Siltec Corporation | Continuous crystal growing furnace |
US4084024A (en) * | 1975-11-10 | 1978-04-11 | J. C. Schumacher Co. | Process for the production of silicon of high purity |
US4249988A (en) * | 1978-03-15 | 1981-02-10 | Western Electric Company, Inc. | Growing crystals from a melt by controlling additions of material thereto |
US4318942A (en) * | 1978-08-18 | 1982-03-09 | J. C. Schumacher Company | Process for producing polycrystalline silicon |
-
1984
- 1984-12-04 WO PCT/US1984/001980 patent/WO1986003523A1/fr not_active Application Discontinuation
- 1984-12-04 EP EP19850900367 patent/EP0205422A4/fr not_active Withdrawn
- 1984-12-04 JP JP60500119A patent/JPS62501497A/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4036595A (en) * | 1975-11-06 | 1977-07-19 | Siltec Corporation | Continuous crystal growing furnace |
US4084024A (en) * | 1975-11-10 | 1978-04-11 | J. C. Schumacher Co. | Process for the production of silicon of high purity |
US4249988A (en) * | 1978-03-15 | 1981-02-10 | Western Electric Company, Inc. | Growing crystals from a melt by controlling additions of material thereto |
US4318942A (en) * | 1978-08-18 | 1982-03-09 | J. C. Schumacher Company | Process for producing polycrystalline silicon |
Non-Patent Citations (1)
Title |
---|
See also references of EP0205422A4 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5126114A (en) * | 1987-12-08 | 1992-06-30 | Nkk Corporation | Manufacturing method and equipment of single silicon crystal |
EP0494312A4 (en) * | 1990-07-26 | 1993-01-20 | Sumitomo Electric Industries, Ltd. | Method and apparatus for making single crystal |
US5290395A (en) * | 1990-07-26 | 1994-03-01 | Sumitomo Electric Industries, Ltd. | Method of and apparatus for preparing single crystal |
DE10250822A1 (de) * | 2002-10-31 | 2004-05-19 | Wacker Siltronic Ag | Verfahren zur Herstellung eines mit leichtflüchtigem Fremdstoff dotierten Einkristalls aus Silicium |
US7070649B2 (en) | 2002-10-31 | 2006-07-04 | Siltronic Ag | Process for producing a silicon single crystal which is doped with highly volatile foreign substances |
DE10250822B4 (de) * | 2002-10-31 | 2006-09-28 | Siltronic Ag | Verfahren zur Herstellung eines mit leichtflüchtigem Fremdstoff dotierten Einkristalls aus Silicium |
CN1317429C (zh) * | 2002-10-31 | 2007-05-23 | 硅电子股份公司 | 制造掺杂高挥发性异物的硅单晶的方法 |
EP1577954A1 (fr) * | 2004-03-09 | 2005-09-21 | RWE SCHOTT Solar GmbH | procédé de transport des particules solides |
Also Published As
Publication number | Publication date |
---|---|
EP0205422A4 (fr) | 1989-06-21 |
JPS62501497A (ja) | 1987-06-18 |
EP0205422A1 (fr) | 1986-12-30 |
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