GB2182262A - Oxygen containing silicon substrates - Google Patents

Oxygen containing silicon substrates Download PDF

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Publication number
GB2182262A
GB2182262A GB08626074A GB8626074A GB2182262A GB 2182262 A GB2182262 A GB 2182262A GB 08626074 A GB08626074 A GB 08626074A GB 8626074 A GB8626074 A GB 8626074A GB 2182262 A GB2182262 A GB 2182262A
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silicon
monocrystal
oxygen concentration
set forth
crucible
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GB2182262B (en
GB8626074D0 (en
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Toshihiko Suzuki
Yasaburo Kato
Motonobu Futagami
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Sony Corp
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Sony Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • 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
    • C30B15/30—Mechanisms for rotating or moving either the melt or the crystal
    • C30B15/305—Stirring of the melt
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Abstract

A method for producing silicon substrates includes growing the silicon crystal body at a relatively high rate of growth. It has been found that the growth rate of the silicon crystal body exerts substantial influence upon generation of crystal defects in the silicon crystal body or silicon substrate. Furthermore, the oxygen concentration in the silicon crystal body or the silicon substrate is significantly higher than in conventional silicon crystals or substrates. The high growth rate of the silicon crystal body suppresses separation of the oxygen from the crystal body. This reduces the number of defects or faults formed in the crystal body during heat treatment during production of the semiconductor devices. In the preferred process, according to the present invention, the growth rate of the silicon crystal body is greater than or equal to 1.2 mm/min. Furthermore, the preferred oxygen concentration in the grown silicon crystal body is selected to be greater than or equal to 1.8 x 10<18> cm<-3>. <IMAGE>

Description

SPECIFICATION High-oxygen-content silicon monocrystal substrate for semiconductor devices and production method therefor BACKGROUND OF THE INVENTION Field ofthe invention The present invention relates generally to a silicon monocrystal substrate capable of absorbing significant metal contamination. In addition, the invention relates two a method for producing a silicon crystal substrate with a significant oxygen concentration. In particular, the invention relates to a method and devicefor producing a high-oxygen-concentration silicon substrate by way of crystal growth.
Description ofthe background art Silicon substrates are widely used for producing various semiconductor devices. In such semiconductor devices, itis generally preferableto minimize leak current. It is known that the leak current can be lowered by an effect called intrinsic gettering (l.G.). The l.G. effect can be achieved as a result of defects formed inthe internal structure ofthe silicon substrate.
As is well known, a silicon substrate is derived from a silicon crystal body prepared by growing a silicon monocrystal from molten polycrystalline silicon by the Czochralski method (hereafter referred to asthe "CZ method"), for instance. In the CZ method, the monocrystal silicon body is drawn slowly out of a bath of molten polycrystal silicon. Silicon substrates are obtained by sectioning or "wafering" the finished silicon monocrystal body.
The finished silicon crystal body contains a great amount of oxygen. The oxygen in the silicon crystal body generates defects or crystal dislocations such as dislocation loops, stacking faults and so forth due to oxygen segregation during heat treatment ofthe silicon substrate. The defects in the finished semiconductor device degrade its rated characteristics in particular, lower its break-down voltage, and increase its leak current. As a result, the production yield of semiconductor devices is significantly lowered.
On the other hand, it has been found that the defects in semiconductor devices may serve to absorb metal contaminants by the so-called intrinsic gettering or I.G. effect. For instance, in semiconductor devices in which the surface of the silicon substrate is the major active region, such as in insulated-gatefield-effect transistors (MOS-FET's) or integrated circuits employing MOS-FET's, defects in the silicon substrate outside of the major active region exhibit the I.G. effect, absorbing metal contaminants from the active regions. This helps reduce the leakage current of the semiconductor devices.
However, there are difficulties in achieving a consistent l.G. effect in mass production. For instance, in cases where the silicon crystal body is grown by the conventional CZ method, the concentration of defects in the crystal body tends to be substantially different atthetop, corresponding to the beginning of growth, than at the bottom, corresponding to the end of growth, due to thermal hysteresis. Furthermore, although a high oxygen concentration is preferable to enhance the I.G. effect, when the oxygen concentration is excessively high, defects tend to form even at the surfaces of the semiconductor devices, resulting in deterioration ofthe characteristics of the semiconductor devices as set forth above.In addition, in some semiconductorproduction processes, attention must be paid to precise control of the oxygen concentration or special l.G.treat- ments must be performed in view of the heat-treatment conditions required for production of some semiconductor devices.
Thus, it is a continuing problem in the art of efficiently manufacturing silicon substrates for semiconductor devices to obtain a substantially high concentration of oxygen, sufficientto enhance the l.G. effect to lower leak current without generating an adverse effect for defects in the finished semiconductor device, especially after heat treatment.
Summary of the invention Therefore, it is a general object of the invention to provide a silicon substrate and production method therefor, which can resolve the problems set forth above.
Another object of the invention is to provide a silicon substrate containing a relatively high concentration of oxygen without deterioration of its characteristics due to oxygen segregation, dislocation loops, stacking faults and so forth.
Afurtherobject of the present invention is to provide a method for producing silicon substrates as a starting material for production of semiconductor devices, which allows high yield without causing deterioration of the characteristics ofthe finished products.
In order to accomplish the above-mentioned and other objects, a method for producing silicon substrates includes growing the silicon crystal body at a speed higherthan is conventionally used. It has been found that the growth rate ofthe silicon crystal body exerts a significant influence on generation of defects in the silicon crystal body. Furthermore, according to the present invention, the oxygen concentration in the silicon crystal body orthesilicon substrate is significantly higherthan in the conventional silicon crystal bodies orsubstrates. Accelerating the growth of the silicon crystal body significantly suppresses separation of the oxygen in the crystal body. This reduces the number of defects or dislocations formed in the crystal body during heat treatment during production of the semiconductor devices.
In the preferred process, according to the present invention, the growth rate ofthe silicon crystal body is greaterthan or equal to 1.2 mm/min. Furthermore, the preferred oxygen concentration in the grown silicon crystal body is greaterthan or equal to 1.8 x 1018 cam~3.
According to the invention, a silicon substrate containing oxygen in concentrations greater than orequalto 18 x 1018 Cm-3 can achieve a leak current less than or equal to 1 x 10-10.
According to one aspect of the invention, a method of producing a silicon substrate containing a substantially high concentration of oxygen for semiconductor devices comprises the steps of: growing a silicon monocrystal from a silicon melt at a substantially high rate of growth selected to prevent loss of oxygen from the monocrystal during subsequent heat treatment during production ofthe semiconductor device, and forming the silicon substrate from the silicon monocrystal.
The preferred growth rate of the silicon monocrystal is greater than or equal to 1.2 mm/min. On the other hand, the preferred oxygen concentration in the silicon substrate is greater than or equal to 1.8 x 018cm-3.
Further preferably, the growth rate of the silicon monocrystal is preferably in the range of approximately 1.5 mm/min. to 2.1 mm/min.
In the preferred embodiment, the silicon monocrystal growth step comprises the steps of: placing silicon in a crucible; heating the silicon so asto maintain the silicon in afluid state; and gradually drawing the silicon monocrystal out ofthe silicon melt in the crucible.
In the step of the silicon, the heat applied thereto is sufficientto prevent the surface ofthe silicon from solidifying. More preferably, in the step of heating the silicon, more heat is applied to the surface of the silicon than to the remainder of the silicon melt.
In an alternative embodiment, the method further comprises the step of applying a magnetic field to the silicon. Furthermore, the preferred method may further comprise the step of driving the crucible to rotate.
The magnetic field applied and/orthe rotation speed of the crucible can be controlled so asto adjustthe oxygen concentration in the silicon substrate.
According to another aspect of the invention, an apparatus for growing a silicon monocrystal containing a substantially high concentration of oxygen as a source for silicon substrates for semiconductor devices, in orderto implement the aforementioned production method for the silicon substrate, comprises a crucible for receiving a silicon, a heater meansforheating the silicon so asto maintain the silicon in afluid state; and a drawing meansfordrawing the silicon monocrystal from the silicon melt in the crucible at a substantially high rate so as to prevent loss of oxygen from the substrate during subsequent heat treatment in a process of fabricating the semiconductor devices.Preferably, the drawing rate of the silicon monocrystal is greaterthan or equal to 1.2 mm/min. In addition, the preferred oxygen concentration in the silicon substrate is greaterthan or equal to 1.8 x 1018 cm -3. The heating means applies sufficient heat to prevent the surface ofthe silicon meltfrom solidifying.The heating means thus applies more heattothe surface ofthe silicon meltthan to the remainder of the silicon melt.
The apparatusfurthercomprises meansforapplying a magneticfield to the silicon melt. In addition,the apparatus may fu rther comprise means for driving the crucible to rotate. The crucible driving means drives the crucible at a variable speed allowing adjustment of the oxygen concentration in the silicon substrate.
According to a further aspect ofthe invention, a semiconductor device is produced from a silicon substrate having an oxygen concentration greaterthan or equal to 1.8 x 1 1018cm3 and having a leakagecurrentvalue lessthan 1 x 10-1 A.
Briefdescription ofthe drawings The present invention will be understood more fully from the detailed description given herebelow and from the accompanying drawings of the preferred embodiment of the invention, which, however, should not betaken to limitthe invention to the specific embodiment but are for explanation and understanding only.
In the drawings: Figure lisa cross-section through a silicon crystal growing apparatus implementing the preferred embodiment ofthe silicon crystal production method according to the invention; Figure2 is a perspective view of part of the heating element of Figure 1; Figure3 is a three-dimensional graph of the observed relationships among the crystal growth rate, the oxygen concentration and stacking fault density; Figure 4 is a graph of heattreatment time versus oxygen concentration; Figures 5and Gshowthe results of measurements of leak current of a number of sample diodes obtained by the silicon substrate production method according to the invention and by a conventionally known process respectively; and Figure 7is a cross-section through a modified embodiment ofthe silicon crystal growing apparatus implementing the preferred embodiment of the silicon crystal production process according to the invention.
Description of the preferred embodiment Referring nowthethe drawings, Figure 1 shows a silicon monocrystal growing apparatus implementing the preferred embodiment of a silicon substrate producing method according to the present invention. As will be seen from Figure 1,the preferred embodiment ofthesilicon substrate producing method includes a processfor growing a silicon monocrystal body as a starting material for silicon substrates. According to the preferred process, the silicon monocrystal is grown bythe CZ method.
In the monocrystal growing apparatus of the present invention, silicon 3 in a quartz crucible 2 disposed within a graphite crucible 1 is melted. A graphite heat generator4 and a heat-insulating material 9 surround the crucible 1. Additional plural cooling jackets 1 0a, 1 0b and 1 Oc surround the insulating material 9. The cooling jacket 10b has a window l2forallowing observation ofthe drawn monocrystal 6. An exhaust pipe 13 is provided in the floor of the cooling jacket 1 Ob for exhausting inert gas serving as an atmosphere introduced into the jackets 10a, 1 Ob and 10cfrom above.A shaft8 fixed to the lower surface ofthe crucible 1 passes loosely through an aperture 1 Od in the floor ofthe cooling jacket 1 Oa and is used to rotate and lift or lowerthe crucible 1.The lower edge ofthe heat generator4 is fixed to a ring plate 14, which in turn is fixed to a pairof shafts 15 passing loosely through two apertures 10e and 10f in thefloorofthe cooling jacket 1 Oa. The shafts 15 are used to lift or lowerthe heatgenerator4. A molybdenum cylindrical heat shield 16with an inner diameter slightly largerthan an outer diameter of the monocrystal 6 is disposed above the liquid silicon 3and around the monocrystal 6. Within the heat shield 16, a seed crystal 5 is held by a chuck7 attached to the lower end of a draw shaft 17 so that a cylindrical monocrystal 6may be grown from the seed crystal 5.
In the CZ method, the maximum monocrystal growth rate Vmax can be expressed as follows, assuming that the solid-liquid interface between the monocrystal 6 and the liquid 3 is flat and no radial temperature gradient exists in the monocrystal 6:
where k denotes thethermal conductivity ofthe monocrystal 6, h denotes the heat of solidification, p denotes the density, and dT/dX denotes the temperature gradient in the solid phase ofthe monocrystal 6 atthe solid-liquid interface. Specifically, X denotes distance along the longitudinal axis ofthe monocrystal 6.In the above expression, since k, hand pare inherent properties ofthe material, it is thus necessary to increase the temperature gradientdT/dX in orderto increase or obtain a large maximum monocrystal growth rate Vmax. In the above-mertioned CZ method, however, since the monocrystal 6 is heated by radiation from the surface of the liquid 3, the innerwall ofthe crucible 2, and the heatgenerator4, the value ofthetemperaturegradient dT/dX is inevitably limited, so that the growth rate has always been relatively small in practice.
As will be appreciated from the above discussion, the growth rate of the silicon monocrystal can be accelerated by reducing the heat applied to the molten silicon 3 by the heat generator 4 and thus lowering the temperature ofthe molten silicon. Although this has a direct proportional effect toward lowering thethermal gradient, by the Stefan-Boltzmann law, the heat radiated toward the monocrystal is reduced to a much grea ter extent, so that the net effect is an increase in the temperature gradient dT/dX. However, reducing the heat generated by the heat generator4in orderto obtain a higher growth rate means thatthe surface ofthe molten silicon will tend to solidify since the surface ofthe molten silicon is cooled by exposure to the gaseousfurnace atmosphere.This limits the extent two which the temperature ofthe molten silicon 3 can be lowered.
The heat generator4 of the preferred silicon monocrystal growing apparatus is designed to apply enough heat to the surface of the molten silicon 3 to maintain the silicon in the liquid state. In particular, the heat generator40fthe preferred construction is designed to apply more heat to the surface ofthe molten silicon thantothe remaining body of molten silicon so asto allowthetemperature ofthe molten silicon 3to be minimized.
Figure2 shows the structure ofthe heat generator4. The heatgenerator4 is made of a conductive material such as graphite, and is generally in the Form of a cylindrical sleeve with atapered portion 4a at its upper end.
The heat generator 4 is formed with alternating upper grooves 4b and lower grooves 4c, each extending parallel tothevertical axis ofthe heatgenerator4. This construction provides the cylindrical shell with a serpentine configuration suitable for use as an electrical heating element. In addition, the upper ends ofthe lower grooves 4c are angularly bifurcated to form two short grooves 4d and 4e extending at an angle of 45" with respect to the groove 4c. Current passes through each section defined by adjoining upper and lower grooves 4b and 4c and generates heat due to ohmic loss.
In order to grow the monocrystal 6 with the seed crystal 5 from the melted silicon material by means ofthe monocrystal growing apparatus constructed asdescribed,thetwo crucibles 1 and 2 are rotated in a clockwise direction by the shaft 8 and the grown monocrystal 6 is rotated by the shaft 17 in a counterclockwise direction, for instance, orviceversa. At the same time, the draw shaft 17 is lifted gradually by means of a driving mechanism (not shown) to draw the monocrystal 6 outofthe melt. Additionally, the two crucibles 1 and 2are both raised gradually so thatthe surface of the liquid 3 can be kept at a predetermined position with respectto the heat generator 4.
The apparatus described above has the following advantages: the upper end 4a ofthe heat generator 4 is tapered and, in addition, the bifurcated grooves 4d and 4e are formed at the upper ends of the lower grooves 4c, and the cross-sectional area ofthetapered portion 4a is smallerthanthe rest ofthe heatgenerator4. In particular, the cross-sectional area near the bifurcated grooves 4d and 4e is quite small. Therefore, as current passes through the heat generator 4, the tapered portion 4a ofthe heat generator 4 is heated to a higher temperature than other portions of the heat generator 4. As a result, the difference in temperature between the melt3a located verticallyoppositethetapered portion 4a and at the innerwall ofthe crucible 2, and the maximum value within the body ofthe melt 3 is small.
Furthermore, since the tapered portion 4a increases the total electrical resistance of the heat generator4 relativeto conventional models, the temperature ofthe heat generator 4 wil I be higher, assuming equal amounts ofcurrent. Therefore, in this embodiment, the currentthrough the heatgenerator4can be smaller than that in conventional heaters of similar design.
As explained, it is necessary to increase the temperature gradient (dT/dX) within the solid-phase monocrystal 6 atthe solid-liquid interface in order to increase the maximum growing speed Vmax. Accordingly, it would be preferable to reduce the heat output ofthe heat generator 4, because the monocrystal is heated by radiation from the heat generator 4.
In the apparatus according to the present invention, even if the heat output of the heat generator4 is reduced in orderto increase the temperature gradient (dT/dX), since the above-mentioned maximum differ- ence in temperature between the surface 3a and the body ofthe melt 3 is small, it is possible to preventthe surface ofthe melt 3 from solidifying at the innerwall ofthe crucible 2. As a result, it is possible to markedly increase the growth rate by as much as 0.2 mm/min,for instance, over conventional systems. Additionally, it is possibleto growthe monocrystal 6 continuously, thus increasing productivity and decreasing the costof monocrystal manufacture.
The preferred embodiment of the method for producing or manufacture the silicon substrate according to the present invention employs the apparatus set forth above. It has been found in the present invention that the crystal growth rate exerts a great influence upon the generation of crystal defects, especially stacking faults. Therefore, in the present invention, the crystal growth rate is set to a value higher than 1.2 mm/min in orderto obtain a silicon crystal bodywith an oxygen concentration of more than 1.8 x 1018cm3. Silicon substrates arethus manufactured by wafering this silicon crystal body.Setting the silicon monocrystal growth rate higher that in the conventional systems prevents segregation of oxygen in succeeding heat treatments and so prevents the accompanying loss of grown silicon monocrystal quality. Therefore, it is possible to increase the oxygen concentration. In the present invention, oxygen concentration of 1.8 x 1018 cm-3 or more, can be achieved and thereby it is possible to obtain an enhanced l.G. effect.
The following discussion is directed to the finished silicon substrate produced by the preferred method according to the invention utilising the apparatus of Figures 1 and 2.
A silicon monocrystal body was drawn and grown by the CZ method. A wafer was cut from the monocrystal body. The surfaces of the wafer wee mirror-polished, and then twice subjected to heat treatment at a temperature of 11 00'C for 2 hours within a dry oxygen atmosphere. Thereafter, the wafer was etched to a depth of 13 m by the so-called dry etching method ro reveal faults. In order to perform this test, various samples were obtained by varying the growth rate ofthe silicon monocrystal body in the CZ process. Also various samples were obtained at various oxygen concentrations. The density of stacking faults in these samples was measured. The results of these measurements are shown in Figure 3.
The results shown in Figure 3 indicate that essentially no stacking faults are formed if silicon monocrystal growth rate is greater than or equal to 1.2 mm/min. Furthermore, it was also confirmed that no stack ing faults are generated during treatment of the silicon wafer orsilicon substrate, including surface polishing.
In addition, the changes in oxygen concentration due to heat treatment at 7500C were measured. Figure 4 shows the results of these measurements in the form of a curve relating oxygen concentration to heattreatmenttime. In the drawing, the curves 21 to 23 represent the relationship between oxygen concentration and heat treatment time at a crystal growth rate of greaterthan 1.2 mm/min. The initial oxygen concentrations for curves 21 to 26 were 1.644 x 1018 cm 1.667:: 1018cm3, 1.709 X o18 cm 1,866:: x 1 o18 cm-3,2.019 x 1018 cm-3,2.019 1018 cm-3, and 1.737 x 1018 cm-3, respectively.Although the oxygen concentration eventually drops as oxygen is driven out ofthe silicon substrate orsilicon monocrystal body by the heattreatment, itis clearthat in the case of the high initial oxygen concentrations due tot he present invention, represented bythe curves 24to 26, the change is small even after a relatively long heat treatment and measurable oxygen loss occurs only after a very long time.
As will be appreciated from Figures 3 and 4, it is clear that high-speed crystal growth results in fewerfaults.
In the nexttest, diodes were prepared by forming a n±Pjunction on silicon substrates obtained bythe present invention and the conventional method, and the p-n junction leak current was measured for each diode. In this case, a p-type region was formed on the n-type silicon substrate, and n+ regions having an area of 2.4 x 1 10-12cm piece/cm2 were formed. The measurement was performed by applying a testing voltage of + 5V to the n+ region.The results of tests on silicon substrates formed from a silicon moncrystal body grown bytheCZ method ata crystal growth rategreaterthan or equal to 1.2 mm/min and which have an oxygen concentration of 2.0 x 1 1018 cm -3, are shown in Figure 5. On the other hand, Figure 6 shows the result ofthe tests performed on silicon substrates formed from a silicon monocrystal body grown by the conventional silicon monocrystal growing method at a crystal growth rate of 0.6 to 0.9 mm/min. in Figures 5and 6, in the abscissa is the measured leak current and the ordinate is the number of samples exhibiting the indicated leak current. As can be understood by a comparison of Figures 5 and 6, the case of silicon substrates manufactu- red bythe present invention,the lead current is reliably decreased to 10-1 1A or less. This may be due to the pronounced I.G. effect produced by the high oxygen concentration.
It should be appreciated that the preferred method according to the present invention can provide a highoxygen-concentration silicon crystal body. It is also possible to accurately selectthe oxygen concentration from awide range by applying a crystal growth method in which a magneticfield is applied to a silicon melt in a quartz crucible and the crucible is rotated as necessary. An example of this crystal growth method employ ing a magneticfield will be explained with reference to Figure7.
In the drawing, the entire apparatus is designated generally by the reference numeral 31. A quartz crucible 32 retains molten silicon from which a crystal is grown. The crucible 32 is rotated about its central axis at an adjustable rotational speed. A heating means 34 surrounds the crucible 32. The heating means 34 may be a cylindrical electric heater35 similarto the heater4 of the previous embodiment. A cylindrical heat insulating body, or a jacket 36 cooled by water, as necessary, is provided outwardly ofthe heating means. Adirect current magneticfield generating means 37 made up of a permanent magnet oran electromagnet is located outwardly of the jacket 36.Asilicon moncrystal seed is designated by the reference numeral 38 while a drawing chuck is shown at reference numeral 39. The drawing chuck 39 raises the silicon monocrystal seed 38 while rotating the seed aboutthe rotational axis ofthe crucible.
The electrical power supply to the heating means 34 is de currentwith 4% or less ripple or a 1 kHzorhigher alternating or pulsating current. This type of current has been proven adequate to prevent unnecessary resonance between the heating means 34 and the magneticfield.
The monocrystalline silicon seed 38 is drawn away from the molten silicon surface at a predetermined speed so as to induce growth of a silicon monocrystal 40. In this case, varying the rotational speed ofthe crucible 32 in particular also changes the oxygen concentration in the finished crystal 40. This is duetothe following reason. The molten silicon in the crucible has an effective viscosity enhanced by application of a magnetic field. Since the silicon is rotated relative to the crucible rotation, frictional contact between the molten silicon 3 and the inner walls ofthe crucible 32 results. Therefore, oxygen in the walls of the crucible 32, specifically of the quartz, is dissolved in the molten silicon 33.The oxygen concentration in the growing crystal 40 thus increases because the dissolved oxygen increases with increasing frictional contact, that is, with increasing rotational speed ofthe crucible relative to the molten silicon 33. Moreover, it has been on firmed that a higher oxygen concentration in the crystal can be achieved, if the rotational speed of the crucible is sufficiently high, when a magneticfield is applied than when no magnetic field is applied.
As described above, since it is possible to maintain a high oxygen concentration, the present invention has many advantages. For instance, the effects of thermal hysteresis as the crystal body is being pulled can be essentially eliminated. Since the oxygen concentration is high, an extremely high l.G. effect can be obtained in heat treatment. In addition, crystal faults in the substrate surface can be suppressed. Because ofthese advantages, in semiconductor elements formed on the silicon substrate many significant advantages are achieved, such as the lowering ofthe leak current, the improvement of breakdown voltage, increased uniformity of characteristics, the improvement of product yield, and so forth.
While the present invention has been disclosed in terms of the preferred embodiment in order to facilitate a better understanding of the invention, it should be appreciated that the invention can be embodied in various ways without departing from the scope of the invention. Therefore, the invention should be understood to include all possible embodiments and modifications to the shown embodiments which can be embodied without departing from the scope ofthe invention set out in the appended claims.

Claims (31)

1. A method of producing a silicon substrate containing a high concentration of oxygen for semiconduc- tor devices comprising the steps of: growing a silicon monocrystal from a silicon melt at a high rate of growth selected to prevent orsubstantially reduce loss of oxygen from the monocrystal during subsequent heattreatmentduring production of said semiconductor device; and forming said silicon substrate from said silicon monocrystal.
2. A method as setforth in claim 1, wherein said growth rate of said silicon monocrystal is greaterthan or equal to 1.2 mm/min.
3. A method as set forth in claim 1, wherein said oxygen concentration in said silicon substrate is greater thanorequalto 1.8 x 1018 cm-3.
4. A method as set forth in claim 2, wherein said oxygen concentration in said silicon substrate is greater than or equal to 1.8 1018 cm-3.
5. A method as set forth in any one of claims 1 to 4, wherein said growth rate of said silicon monocrystal is preferably in the range of approximately 1.5mm/min. 2.1 mm/min.
6. A method as set forth in anyone ofthe preceding claims, wherein said silicon monocrystal growth step comprises the steps of: placing silicon in a crucible; heating said silicon so asto maintain said silicon in afluid state; and gradually drawing said silicon monocrystal out of said silicon melt in said crucible.
7. A method as setforth in claim 6, wherein in said step of heating said silicon, the heat applied thereto is sufficientto prevent the surface of said silicon from solidifying.
8. A method as setforth in claim 7, wherein in said step of heating said silicon, more heat is applied to said surface of said silicon than to the remainder of said silicon melt.
9. A method as setforth in claims 6,7 or 8, which further comprises the step of applying a magneticfieldto said silicon so asto control the oxygen concentration.
10. A method as set forth in any one of claims 6to 9which further comprises the step of driving said crucible to rotate.
11. A method as set forth in claim 10, wherein the rotation speed of said crucible is controlled so asto adjustthe oxygen concentration in said silicon substrate.
12. An apparatus for growing a silicon monocrystal containing a high concentration of oxygen as a source for silicon substrates for semiconductor devices, comprising: a crucible for receiving a silicon; a heater means for heating said silicon so asto maintain said silicon in afluid state; and a drawing means for drawing said silicon monocrystal from the silicon melt in said crucible at a high rate so asto prevent or substantially reduce loss of oxygen from said substrate during subsequent heat treatment in a process of fabricating said semiconductor devices.
13. An apparatus as set forth in claim 12, wherein said drawing rate of said silicon monocrystal is grater than orequal to 1.2 mm/min.
14. An apparatus as set forth in claim 13, wherein said oxygen concentration in said silicon substrate is greaterthan orequal to 1.8 x 1018cm3.
15. An apparatus as setforth in claim 13 or 14, wherein the growth rate of said silicon monocrystal is preferably in the range of approximately 1 ,Smm/min. to 2.1 mm/min.
16. An apparatus assetforth in any one of claims 12to 15, wherein said heating means applies sufficient heat to prevent the surface of said silicon melt from solidifying.
17. An apparatus as set forth in claim 16, wherein said heating means applies more heatto said surface of said silicon meltthan to the remainder of said silicon melt.
18. An apparatus as setforth in any one of claims 12to 17, which further comprises means for applying a magneticfield to said silicon melt so as to control the oxygen concentration.
19. An apparatus assetforth in any one of claims 12to 18, which further comprises means for driving said crucible to rotate.
20. An apparatus as set forth in claim 19, wherein said crucible driving means drives said crucible art a variable speed allowing adjustment of said oxygen concentration in said silicon substrate.
21. A semiconductor device produced from a silicon substrate having an oxygen concentration greater than or equal to 1.8 x 1018cm3 and having a leak current value less than 1 x 10-'OA.
22. A method for producing a silicon substrate with enhanced oxygen concentration comprising the steps of: growing a silicon monocrystal from a silicon melt at an effective accelerated rate of growth to reducethe number of defects formed during subsequent heat treatment, to thus suppress separation of oxygen in the crystal body and to increase the oxygen in the crystal body, whereby leak current is reduced, said accelerated rate of growth being related to said enhanced oxygen concentration; and forming said silicon substrate from said silicon monocrystal.
23. The method as set forth in claim 22, wherein said accelerated growth rate is at least 1 .2mm/min. and the oxygen concentration is at least 1.8 x 1018cm-3.
24. The method as set forth in claim 23, wherein said accelerated growth rate is in a range of about 1.5 mm/mintoabout2.1 mm/min.
25. The method as set forth in claim 22,23 or24wherein said growing step includes the step of applying more heatto a surface of the silicon meltthan to the remainder of said meltto preventthe surface ofsaid silicon melt from solidifying.
26. Amethod as set forth in any one of claims 22to 25, further including the step of applying a magnetic field to the silicon so as to control the oxygen concentration.
27. Amethod as set forth in anyone of claims 22to 26, further including the step of rotating a crucible contrary to said monocrystal.
28. A method as set forth in claim 27, further including the step of controlling the speed of rotation of said crucible to adjust the oxygen concentration in the silicon substrate.
29. A method of producing a silicon substrate substantially as hereinbefore described with reference to and as illustrated in the accompanying drawings.
30. Apparatus for growing a silicon monocrystal, such apparatus being constructed and arranged to operate substantially as herein before described with reference to and as illustrated in the accompanying drawings.
31. A semiconductor device produced from a silicon substrate, the substrate having been made using the method ofanyone of claims 1 toll and 22to 29 orthe apparatus ofanyone of claims 12to 21 and 30.
GB8626074A 1985-10-31 1986-10-31 High-oxygen-content silicon monocrystal substrate for semiconductor devices and production method therefor Expired GB2182262B (en)

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US6416836B1 (en) 1998-10-14 2002-07-09 Memc Electronic Materials, Inc. Thermally annealed, low defect density single crystal silicon
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EP0503816A1 (en) * 1991-03-15 1992-09-16 Shin-Etsu Handotai Company Limited Heat treatment of Si single crystal
US5834322A (en) * 1991-03-15 1998-11-10 Shin-Etsu Handotai Co., Ltd. Heat treatment of Si single crystal
US5976246A (en) * 1996-03-27 1999-11-02 Shin-Etsu Handotai Co., Ltd. Process for producing silicon single crystal
EP0829561A1 (en) * 1996-03-27 1998-03-18 Shin-Etsu Handotai Co., Ltd. Process for producing silicon single crystal
EP0829561A4 (en) * 1996-03-27 1999-06-02 Shinetsu Handotai Kk Process for producing silicon single crystal
EP0866150A1 (en) * 1997-03-21 1998-09-23 Wacker Siltronic Gesellschaft für Halbleitermaterialien Aktiengesellschaft Apparatus and process for pulling a single crystal
US6153008A (en) * 1997-03-21 2000-11-28 Wacker Siltronic Gesellschaft Fur Halbleitermaterialien Ag Device and method for pulling a single crystal
US6379642B1 (en) 1997-04-09 2002-04-30 Memc Electronic Materials, Inc. Vacancy dominated, defect-free silicon
US6409826B2 (en) 1997-04-09 2002-06-25 Memc Electronic Materials, Inc. Low defect density, self-interstitial dominated silicon
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US6190631B1 (en) 1997-04-09 2001-02-20 Memc Electronic Materials, Inc. Low defect density, ideal oxygen precipitating silicon
US6632278B2 (en) 1997-04-09 2003-10-14 Memc Electronic Materials, Inc. Low defect density epitaxial wafer and a process for the preparation thereof
US6254672B1 (en) 1997-04-09 2001-07-03 Memc Electronic Materials, Inc. Low defect density self-interstitial dominated silicon
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US7442253B2 (en) 1997-04-09 2008-10-28 Memc Electronic Materials, Inc. Process for forming low defect density, ideal oxygen precipitating silicon
EP1118697A3 (en) * 1997-04-09 2001-09-05 MEMC Electronic Materials, Inc. Low defect density, vacancy dominated silicon
US6287380B1 (en) 1997-04-09 2001-09-11 Memc Electronic Materials, Inc. Low defect density silicon
US6605150B2 (en) 1997-04-09 2003-08-12 Memc Electronic Materials, Inc. Low defect density regions of self-interstitial dominated silicon
US6896728B2 (en) 1997-04-09 2005-05-24 Memc Electronic Materials, Inc. Process for producing low defect density, ideal oxygen precipitating silicon
US6555194B1 (en) 1997-04-09 2003-04-29 Memc Electronic Materials, Inc. Process for producing low defect density, ideal oxygen precipitating silicon
US7229693B2 (en) 1997-04-09 2007-06-12 Memc Electronic Materials, Inc. Low defect density, ideal oxygen precipitating silicon
WO1998045509A1 (en) * 1997-04-09 1998-10-15 Memc Electronic Materials, Inc. Low defect density silicon
US6409827B2 (en) 1997-04-09 2002-06-25 Memc Electronic Materials, Inc. Low defect density silicon and a process for producing low defect density silicon wherein V/G0 is controlled by controlling heat transfer at the melt/solid interface
EP0943703A3 (en) * 1998-03-20 2002-03-20 Shin-Etsu Handotai Company Limited Silicon single crystal and method for producing the same
EP0943703A2 (en) * 1998-03-20 1999-09-22 Shin-Etsu Handotai Company Limited Silicon single crystal and method for producing the same
US6913647B2 (en) 1998-06-26 2005-07-05 Memc Electronic Materials, Inc. Process for cooling a silicon ingot having a vacancy dominated region to produce defect free silicon
US6562123B2 (en) 1998-06-26 2003-05-13 Memc Electronic Materials, Inc. Process for growing defect-free silicon wherein the grown silicon is cooled in a separate chamber
US6328795B2 (en) 1998-06-26 2001-12-11 Memc Electronic Materials, Inc. Process for growth of defect free silicon crystals of arbitrarily large diameters
US6849901B2 (en) 1998-09-02 2005-02-01 Memc Electronic Materials, Inc. Device layer of a silicon-on-insulator structure having vacancy dominated and substantially free of agglomerated vacancy-type defects
US6342725B2 (en) 1998-09-02 2002-01-29 Memc Electronic Materials, Inc. Silicon on insulator structure having a low defect density handler wafer and process for the preparation thereof
US6236104B1 (en) 1998-09-02 2001-05-22 Memc Electronic Materials, Inc. Silicon on insulator structure from low defect density single crystal silicon
US6312516B2 (en) 1998-10-14 2001-11-06 Memc Electronic Materials, Inc. Process for preparing defect free silicon crystals which allows for variability in process conditions
US6416836B1 (en) 1998-10-14 2002-07-09 Memc Electronic Materials, Inc. Thermally annealed, low defect density single crystal silicon
US6284039B1 (en) 1998-10-14 2001-09-04 Memc Electronic Materials, Inc. Epitaxial silicon wafers substantially free of grown-in defects
US6652646B2 (en) 1998-10-14 2003-11-25 Memc Electronic Materials, Inc. Process for growing a silicon crystal segment substantially free from agglomerated intrinsic point defects which allows for variability in the process conditions
US6743289B2 (en) 1998-10-14 2004-06-01 Memc Electronic Materials, Inc. Thermal annealing process for producing low defect density single crystal silicon
US6565649B2 (en) 1998-10-14 2003-05-20 Memc Electronic Materials, Inc. Epitaxial wafer substantially free of grown-in defects
US6500255B2 (en) 1998-10-14 2002-12-31 Memc Electronic Materials, Inc. Process for growing silicon crystals which allows for variability in the process conditions while suppressing the formation of agglomerated intrinsic point defects
US7097718B2 (en) 1998-10-14 2006-08-29 Memc Electronic Materials, Inc. Single crystal silicon wafer having an epitaxial layer substantially free from grown-in defects
US7105050B2 (en) 2000-11-03 2006-09-12 Memc Electronic Materials, Inc. Method for the production of low defect density silicon
US6858307B2 (en) 2000-11-03 2005-02-22 Memc Electronic Materials, Inc. Method for the production of low defect density silicon
US7217320B2 (en) 2001-01-26 2007-05-15 Memc Electronics Materials, Inc. Low defect density silicon having a vacancy-dominated core substantially free of oxidation induced stacking faults
US6846539B2 (en) 2001-01-26 2005-01-25 Memc Electronic Materials, Inc. Low defect density silicon having a vacancy-dominated core substantially free of oxidation induced stacking faults
US8216362B2 (en) 2006-05-19 2012-07-10 Memc Electronic Materials, Inc. Controlling agglomerated point defect and oxygen cluster formation induced by the lateral surface of a silicon single crystal during CZ growth
US8673248B2 (en) 2006-05-19 2014-03-18 Memc Electronic Materials, Inc. Silicon material with controlled agglomerated point defects and oxygen clusters induced by the lateral surface

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AU597599B2 (en) 1990-06-07
DK518486D0 (en) 1986-10-30
CN86106346A (en) 1987-06-17
FR2589489B1 (en) 1994-06-10
FR2589489A1 (en) 1987-05-07
SE8604627D0 (en) 1986-10-30
CN1016191B (en) 1992-04-08
AU6455086A (en) 1987-05-07
CA1336061C (en) 1995-06-27
SE8604627L (en) 1987-05-01
DK518486A (en) 1987-05-01
GB2182262B (en) 1989-09-27
IT8648592A0 (en) 1986-10-28
GB8626074D0 (en) 1986-12-03
NL8602738A (en) 1987-05-18
MY100449A (en) 1990-10-15
IT1198454B (en) 1988-12-21
JPS62105998A (en) 1987-05-16
DE3637006A1 (en) 1987-05-07
ATA289086A (en) 1996-01-15
KR870004498A (en) 1987-05-09

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