WO2012008087A1 - シリコン基板の製造方法及びシリコン基板 - Google Patents
シリコン基板の製造方法及びシリコン基板 Download PDFInfo
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- WO2012008087A1 WO2012008087A1 PCT/JP2011/003188 JP2011003188W WO2012008087A1 WO 2012008087 A1 WO2012008087 A1 WO 2012008087A1 JP 2011003188 W JP2011003188 W JP 2011003188W WO 2012008087 A1 WO2012008087 A1 WO 2012008087A1
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Images
Classifications
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections
- H01L21/3221—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections of silicon bodies, e.g. for gettering
- H01L21/3225—Thermally inducing defects using oxygen present in the silicon body for intrinsic gettering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
- H01L29/0684—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape, relative sizes or dispositions of the semiconductor regions or junctions between the regions
-
- 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
Definitions
- the present invention relates to a method of manufacturing a silicon substrate and a silicon substrate manufactured by the method.
- CZ method silicon single crystal grown by the CZ method
- oxygen of about 10-20 ppma JEIDA: using a conversion factor by the Japan Electronics Industry Promotion Association
- the crystal is supersaturated in the course of cooling, and aggregates to form oxygen precipitates (hereinafter referred to as glow-in oxygen precipitates) when the crystal temperature becomes 700 ° C. or lower.
- oxygen precipitates hereinafter referred to as glow-in oxygen precipitates
- the size is extremely small, and TZDB (Time Zero Dielectric Breakdown) characteristics and device characteristics that are one of oxide breakdown voltage characteristics and device characteristics are not deteriorated at the shipping stage. Defects due to single crystal growth that deteriorate the oxide breakdown voltage characteristics and device characteristics are vacancy-type points called vacancy (hereinafter sometimes abbreviated as Va) taken into the silicon single crystal from the crystal melt.
- Va vacancy
- I interstitial-silicon
- FIG. 4 shows the average value G (° C./mm) of the temperature gradient in the crystal in the pulling axis direction in the temperature range from the silicon melting point to 1300 ° C. by changing the pulling rate V (mm / min) during single crystal growth. It is a figure which shows the defect area
- the temperature distribution in the single crystal depends on the structure in the CZ furnace (hereinafter referred to as hot zone (HZ)), and the distribution hardly changes even if the pulling rate is changed.
- HZ hot zone
- V / G corresponds to only a change in pulling speed. That is, the pulling speed V and V / G are approximately directly proportional. Therefore, the pulling speed V is used on the vertical axis of FIG.
- the BMD as described above occurs on the surface of the silicon substrate which is the device active region, it adversely affects the device characteristics such as junction leakage.
- it exists in the bulk other than the device active region it is mixed in the device process This is effective because it functions as a gettering site for capturing metal impurities.
- RTP Rapid Thermal Process
- This RTP treatment is a nitride film formation atmosphere on a silicon substrate or a mixed gas atmosphere of a nitride film formation atmosphere gas and a non-nitride film formation gas such as a noble gas or a reducing gas, for example, 50 ° C./sec.
- This is a heat treatment method in which the temperature is rapidly raised from room temperature at a rate of temperature rise, heated and held at a temperature of about 1200 ° C.
- Va is injected from the surface of the silicon substrate while maintaining a high temperature of, for example, 1200 ° C. in an N 2 atmosphere, and the temperature range from 1200 ° C. to 700 ° C. is cooled at a rate of temperature decrease of, for example, 5 ° C./sec. Then, redistribution due to diffusion of Va and disappearance of I occur. As a result, Va is unevenly distributed in the bulk.
- the silicon substrate in such a state is heat-treated at, for example, 800 ° C., oxygen rapidly clusters in a high Va concentration region, but oxygen does not cluster in a low Va concentration region. In this state, when heat treatment is performed at a temperature of 1000 ° C. for a certain time, clustered oxygen grows to form BMD.
- BMD having a distribution in the depth direction of the silicon substrate is formed according to the concentration profile of Va formed by RTP treatment. Therefore, by controlling the conditions such as the atmosphere, maximum temperature, and holding time of the RTP process, a desired Va concentration profile is formed on the silicon substrate, and then an oxygen precipitation heat treatment is performed on the obtained silicon substrate.
- a silicon substrate having a desired DZ width and BMD profile in the depth direction can be manufactured.
- Patent Document 3 discloses that when RTP treatment is performed in an oxygen gas atmosphere, an oxide film is formed on the surface, and I is injected from the oxide film interface, so that BMD formation is suppressed.
- the RTP treatment can promote BMD formation or conversely, depending on conditions such as the atmospheric gas and the maximum holding temperature.
- the annealing since the annealing is performed for a very short time, almost no outward diffusion of oxygen occurs, and a decrease in oxygen concentration at the surface layer can be ignored.
- Patent Document 4 describes a method in which a silicon substrate having an entire surface made of an N region is cut out from a single crystal in an N region where Va and I aggregates are not present as a silicon substrate.
- this method since there is no glow-in defect in Si as a material, it can be considered that it can be easily made defect-free by RTP treatment.
- the TDDB characteristic which is the long-term reliability characteristic of the oxide film after measurement, is measured, the TZDB characteristic is hardly lowered in the Nv region of the silicon substrate, but the TDDB characteristic may be lowered.
- the region where the TDDB characteristic is deteriorated is a region where the defect detected by the RIE method exists in the Nv region, a silicon substrate having no RIE defect on the surface layer and its manufacture Method development is extremely important.
- the crystal defect evaluation method by this RIE method will be explained.
- the RIE method is a method for evaluating a minute crystal defect containing silicon oxide (hereinafter referred to as SiOx) in a semiconductor single crystal substrate while providing resolution in the depth direction.
- SiOx silicon oxide
- Patent Document 6 The method disclosed in Patent Document 6 is known. It has been.
- This method evaluates crystal defects by performing highly selective anisotropic etching such as reactive ion etching at a constant thickness on the main surface of the substrate and detecting the remaining etching residue. is there. Since the etching rate is different between the crystal defect forming region containing SiOx and the non-forming region not containing (the former has a lower etching rate), when the reactive ion etching is performed, the main surface of the substrate is formed. Remains a cone-shaped hillock with a crystal defect containing SiOx as a vertex. Crystal defects are emphasized in the form of protrusions by anisotropic etching, and even minute defects can be easily detected.
- highly selective anisotropic etching such as reactive ion etching at a constant thickness on the main surface of the substrate and detecting the remaining etching residue. is there. Since the etching rate is different between the crystal defect forming region containing SiOx and the non-forming region not containing (the former has a lower etching
- the depletion layer expands. If a defect such as BMD is present in this depletion layer region, it causes junction leakage. For these reasons, it is required that the substrate surface layer (especially, the region from the surface to 3 ⁇ m), which is the operation region of many devices, does not have glow-in defects such as COP, BMD, and glow-in oxygen precipitates. Yes.
- the oxygen concentration below the solid solubility limit. For example, it can be achieved by a method of heat treatment at 1100 ° C. or more and lowering the oxygen concentration of the surface layer by utilizing the outward diffusion of oxygen, so that the oxygen concentration of the surface layer is reduced by the outward diffusion of oxygen.
- the mechanical strength of the surface layer is also lowered.
- lifetime is reduced by the formation of defect levels due to metal impurities, oxygen precipitation, vacancies, and the like. Therefore, in order to ensure the function of the semiconductor element stably, it is necessary to manufacture the silicon substrate so that the lifetime is at least 500 ⁇ sec.
- the present inventor has found that RIE defects on the surface of the silicon substrate can be eliminated by RTP treatment at a temperature higher than 1300 ° C.
- the lifetime after the heat treatment is greatly reduced in the silicon substrate subjected to RTP treatment at a temperature higher than 1300 ° C.
- the lifetime is less than 500 ⁇ sec, there is a high possibility of a device failure, which causes a problem.
- the present invention has been made in view of the above problems, and is a defect (RIE defect) detected by an RIE method such as oxygen precipitates, COP, OSF, etc., at a depth of at least 1 ⁇ m from the surface to be a device fabrication region. ) And a lifetime of 500 ⁇ sec or more, and a silicon substrate manufactured by the method.
- RIE defect a defect detected by an RIE method such as oxygen precipitates, COP, OSF, etc.
- the present invention is a method for manufacturing a silicon substrate, and at least a rapid heating / rapid cooling device is provided on a silicon substrate cut out from a silicon single crystal ingot grown by the Czochralski method. Used in a first atmosphere containing at least one of a nitride film forming atmosphere gas, a rare gas and an oxidizing gas, and held at a first temperature higher than 1300 ° C.
- a method for manufacturing a silicon substrate comprising: a second heat treatment step for performing a rapid heat treatment on the silicon substrate at the controlled second temperature and second atmosphere.
- the first temperature is rapidly increased from the first temperature to the second temperature lower than 1300 ° C. at a temperature lowering rate of 5 ° C./sec to 150 ° C./sec. It is preferable to perform the second heat treatment step by lowering the temperature and subjecting the silicon substrate to a rapid heat treatment while maintaining the second temperature at the second temperature for 1-60 seconds.
- the second heat treatment step by performing the rapid heat treatment, the vacancy concentration inside the silicon substrate can be efficiently reduced, and the generation of defects due to vacancies can be effectively suppressed. It is possible to reliably prevent the lifetime from decreasing.
- the second atmosphere in the second heat treatment step is an atmosphere containing at least one kind of gas of a rare gas and a nitride film forming atmosphere gas, and the second temperature is set to be 300 ° C. or higher and lower than 1300 ° C. be able to.
- the atmosphere includes at least one kind of a rare gas and a nitride film forming atmosphere gas, a silicon substrate on which sufficient BMD is deposited in the device manufacturing process can be obtained.
- the second atmosphere in the second heat treatment step may be an atmosphere of a reducing gas or a mixed gas of a reducing gas and a rare gas
- the second temperature may be 300 ° C. or higher and lower than 900 ° C.
- the second atmosphere in the second heat treatment step may be an oxidizing gas atmosphere, and the second temperature may be 300 ° C. or higher and 700 ° C. or lower, or 1100 ° C. or higher and lower than 1300 ° C.
- the silicon substrate is a silicon single crystal wafer cut from a silicon single crystal ingot whose entire surface is an OSF region and whose entire surface is an N region, or a region where the OSF region and the N region are mixed.
- a silicon single crystal wafer cut from a silicon single crystal ingot whose entire surface is an OSF region and whose entire surface is an N region, or a region where the OSF region and the N region are mixed.
- the present invention is a silicon substrate manufactured by the method for manufacturing a silicon substrate of the present invention, wherein there is a defect detected by the RIE method at a depth of at least 1 ⁇ m from the surface of the silicon substrate which is a device manufacturing region.
- the present invention provides a silicon substrate characterized in that the lifetime of the silicon substrate is 500 ⁇ sec or more. With such a silicon substrate, there is no device characteristic defect due to a defect in the device fabrication region or a reduction in lifetime, and a high-quality device fabrication substrate is obtained.
- a second temperature for subsequently suppressing the generation of defects due to vacancies as a second heat treatment.
- the present invention has been completed by finding that rapid thermal processing is performed in the second atmosphere. As a result, the lifetime can be prevented from decreasing as well as the surface layer defect disappears, so that a high-quality silicon substrate free from device defects can be manufactured.
- FIG. 1 is a schematic view showing a silicon single crystal pulling apparatus.
- FIG. 2 is a schematic view showing a single-wafer rapid heating / cooling device.
- a silicon single crystal ingot is first grown and a silicon substrate is cut out from the silicon single crystal ingot.
- the diameter of the silicon single crystal ingot to be grown is not particularly limited, and can be, for example, 150 mm to 300 mm or more, and can be grown to a desired size in accordance with the application.
- the defect region of the silicon single crystal ingot to be grown for example, a V-Rich region, an OSF region, an N region, or a region in which these regions are mixed can be grown. Then, a silicon single crystal ingot in which the entire surface is an OSF region and the entire surface is an N region, or a region where the OSF region and the N region are mixed is grown. Even in the case of a silicon substrate cut out from a silicon single crystal ingot including a V-Rich region where COP or the like is likely to occur, the present invention can greatly reduce defects.
- a silicon substrate cut out from a silicon single crystal ingot whose entire surface is an OSF region, and whose entire surface is an N region, or a region where the OSF region and the N region are mixed, it hardly contains a COP that hardly disappears.
- the rapid heat treatment of the present invention is particularly effective because defects can be surely eliminated and RIE defects at deeper positions can be easily eliminated.
- FIG. 1 shows a single crystal pulling apparatus 10.
- the single crystal pulling apparatus 10 includes a pulling chamber 11, a crucible 12 provided in the pulling chamber 11, a heater 14 disposed around the crucible 12, a crucible holding shaft 13 for rotating the crucible 12, and a rotation mechanism thereof. (Not shown), a seed chuck 21 that holds a seed crystal of silicon, a wire 19 that pulls up the seed chuck 21, and a winding mechanism (not shown) that rotates or winds the wire 19. ing.
- the crucible 12 is provided with a quartz crucible on the inner side containing the silicon melt (hot water) 18 and on the outer side with a graphite crucible.
- a heat insulating material 15 is disposed around the outside of the heater 14.
- annular graphite tube (rectifying tube) 16 may be provided as shown in FIG. 1, or an annular outer heat insulating material (not shown) may be provided on the outer periphery of the solid-liquid interface 17 of the crystal.
- a cylindrical cooling device that blows cooling gas or cools the single crystal by blocking radiant heat.
- a magnet (not shown) is installed outside the pulling chamber 11 in the horizontal direction, and a magnetic field in the horizontal direction or the vertical direction is applied to the silicon melt 18, thereby suppressing convection of the melt and a single crystal.
- MCZ method apparatus for achieving stable growth. Each part of these apparatuses can be the same as that of the prior art, for example.
- a high-purity polycrystalline raw material of silicon is heated to a melting point (about 1420 ° C.) or higher and melted.
- a melting point about 1420 ° C.
- the tip of the seed crystal is brought into contact with or immersed in the approximate center of the surface of the silicon melt 18.
- the crucible holding shaft 13 is rotated in an appropriate direction, and the wire 19 is wound while being rotated, and the seed crystal is pulled up to start growing the silicon single crystal ingot 20.
- the pulling speed and temperature are appropriately adjusted so that a desired defect region is obtained, and a substantially cylindrical silicon single crystal ingot 20 is obtained.
- the silicon single crystal ingot can be manufactured again so that a desired defect region can be obtained by controlling the pulling rate in this test.
- the silicon single crystal ingot thus manufactured can be sliced, polished, etc., for example, to obtain a silicon substrate.
- the silicon substrate obtained in this manner is a first atmosphere containing at least one of a nitride film forming atmosphere gas, a rare gas, and an oxidizing gas using a rapid heating / cooling apparatus.
- a first heat treatment step is performed in which rapid heat treatment is performed by holding at a first temperature higher than 1300 ° C. and lower than the melting point of silicon for 1-60 seconds.
- the heat treatment temperature is higher than 1300 ° C., the RIE defect at least 1 ⁇ m deep from the surface of the silicon substrate can be surely eliminated, and the defect appears on the surface to be the device fabrication region. In this way, device failure can be prevented.
- the rapid heat treatment time in the first heat treatment step is kept for 1 to 60 seconds, and in particular, by setting the upper limit to 60 seconds, there is almost no deterioration in productivity, so there is no increase in cost. Moreover, the occurrence of slip dislocation during the rapid heat treatment can be reliably prevented. Further, since the outward diffusion of oxygen can be moderated during the heat treatment and a large decrease in oxygen concentration can be prevented from occurring on the surface layer, a decrease in mechanical strength can be prevented. Also, in the above atmosphere, RIE defects on the substrate surface layer can be eliminated, and at the same time, point defects such as new vacancies can be uniformly formed inside the substrate. Is greatly promoted, and a silicon substrate having a high gettering ability can be manufactured. In the case of an atmosphere containing an oxidizing gas, BMD formation during device heat treatment is suppressed depending on the concentration. Thus, the atmosphere can be adjusted to control the formation of BMD during device heat treatment.
- FIG. 2 shows a schematic diagram of an example of a rapid heating / rapid cooling apparatus that can be used.
- the rapid heating / cooling device 52 has a chamber 53 made of quartz, and the silicon substrate W can be rapidly heat-treated in the chamber 53. Heating is performed by a heating lamp 54 (for example, a halogen lamp) disposed so as to surround the chamber 53 from above, below, left, and right.
- the heating lamps 54 can control power supplied independently.
- an auto shutter 55 is provided to block outside air.
- the auto shutter 55 is provided with a wafer insertion opening (not shown) that can be opened and closed by a gate valve. Further, the auto shutter 55 is provided with a gas exhaust port 51 so that the furnace atmosphere can be adjusted.
- the silicon substrate W is disposed on a three-point support portion 57 formed on the quartz tray 56.
- a quartz buffer 58 is provided on the gas inlet side of the quartz tray 56, and can prevent an introduced gas such as an oxidizing gas, a nitriding gas, and an Ar gas from directly hitting the silicon substrate W. .
- the chamber 53 is provided with a temperature measurement special window (not shown), and the pyrometer 59 installed outside the chamber 53 can measure the temperature of the silicon substrate W through the special window.
- the second temperature and the second atmosphere for suppressing the generation of defects due to vacancies inside the silicon substrate are controlled, and the control is performed on the silicon substrate.
- a second heat treatment step is performed in which rapid heat treatment is performed at the second temperature and the second atmosphere.
- Such a second heat treatment step can suppress the formation of defect aggregation due to vacancy agglomeration and vacancies and prevent the lifetime from greatly decreasing.
- a silicon substrate having a time of 500 ⁇ sec or more can be obtained.
- the temperature is rapidly lowered from the first temperature to a second temperature lower than 1300 ° C. at a temperature drop rate of 5 ° C./sec or more and 150 ° C./sec or less. It is preferable to perform the second heat treatment step by subjecting the substrate to a rapid heat treatment by holding at a second temperature for 1-60 seconds. If the second heat treatment step is performed under the above-described conditions, it is possible to efficiently achieve the reduction of the vacancy concentration and the suppression of the formation of defect levels due to the vacancies, and effectively prevent the lifetime from decreasing. be able to.
- the second atmosphere in the second heat treatment step can be an atmosphere containing at least one kind of a rare gas and a nitride film forming atmosphere gas, and the second temperature can be set to 300 ° C. or higher and lower than 1300 ° C. .
- the second atmosphere is an atmosphere containing at least one kind of a rare gas and a nitride film forming atmosphere gas, the BMD formation during the device heat treatment is further promoted.
- the second temperature in the atmosphere is particularly preferably 300 ° C. or higher and 900 ° C. or lower or 1100 ° C. or higher and 1250 ° C. or lower. If it is the temperature of the said range, aggregation of a void
- the second atmosphere in the second heat treatment step may be an atmosphere of a reducing gas or a mixed gas of a reducing gas and a rare gas
- the second temperature may be 300 ° C. or higher and lower than 900 ° C.
- the atmosphere is a reducing gas or a mixed gas of a reducing gas and a rare gas
- BMD formation during device heat treatment is further promoted. If the second temperature is less than 900 ° C., slip dislocation is difficult to enter, which is preferable.
- the reducing gas is hydrogen
- hydrogen is injected into the substrate.
- Hydrogen causes a donor to be formed by heat treatment in a device process, and such a donor causes a decrease in lifetime and a change in substrate resistivity.
- the temperature of the heat treatment in the device process has been lowered, and it is not preferable that hydrogen that causes the formation of donors is distributed at a high concentration in the silicon substrate. Therefore, in the temperature range of 300 ° C. or higher and lower than 900 ° C. If the second heat treatment step of the present invention is performed, the implanted hydrogen has a low concentration, so there is no problem.
- the second atmosphere in the second heat treatment step may be an oxidizing gas atmosphere
- the second temperature may be 300 ° C. or higher and 700 ° C. or lower, or 1100 ° C. or higher and lower than 1300 ° C.
- the effect of suppressing the aggregation of pores is low at a heat treatment temperature higher than 700 ° C. and lower than 1100 ° C., but in the temperature range of 300 ° C. or higher and 700 ° C. or lower, or 1100 ° C. or higher and lower than 1300 ° C. If there is, it is possible to effectively suppress the agglomeration of vacancies and reliably suppress the defects due to the vacancies.
- the nitride film forming atmosphere gas that can be used in the present invention
- N 2 gas, NH 3 gas, or the like can be used.
- Ar gas can be used as the reducing gas.
- H 2 gas can be used as the oxidizing gas, for example, gas containing O 2 .
- the gas is not limited to the above type.
- the second temperature and atmosphere controlled by the second heat treatment step are not particularly limited as long as they can suppress generation of defects due to vacancies.
- the silicon substrate is taken out from the rapid heating / rapid cooling device once, and then the second heat treatment step may be performed, or the second heat treatment step may be performed a plurality of times to obtain the effects of the present invention. be able to.
- the silicon substrate manufactured by the silicon substrate manufacturing method of the present invention as described above, there is no defect detected by the RIE method at a depth of at least 1 ⁇ m from the surface of the silicon substrate as a device manufacturing region, In addition, it becomes a high-quality device manufacturing substrate in which the lifetime of the silicon substrate is 500 ⁇ sec or more.
- Example and comparative examples A silicon single crystal pulling apparatus shown in FIG. 1 is used to apply a transverse magnetic field to grow an N region silicon single crystal ingot (diameter 12 inches (300 mm), orientation ⁇ 100>, conductive p-type) by the MCZ method.
- CP treatment Chemical Passivation treatment
- Another wafer was subjected to a simulation heat treatment of the flash memory manufacturing process to form a BMD in the wafer. Then, it was immersed in 5% HF, and the oxide film formed on the surface was removed. Thereafter, etching was performed with an RIE apparatus, and the number of residual protrusions was measured using an electron microscope to calculate the defect density.
- a graph showing the relationship between the calculated BMD density and the temperature and atmosphere of the second heat treatment step is shown in FIG. As shown in FIG.
- the BMD density of the wafer subjected to the rapid heat treatment in an atmosphere other than the O 2 gas atmosphere is high as a whole, while the BMD density of the wafer subjected to the rapid heat treatment in the O 2 gas atmosphere is BMD Formation was suppressed and was below the lower limit of detection.
- the BMD formation during the device fabrication heat treatment can be easily controlled by the atmosphere.
- a silicon single crystal pulling apparatus shown in FIG. 1 is used to apply a transverse magnetic field to grow an N region silicon single crystal ingot (diameter 12 inches (300 mm), orientation ⁇ 100>, conductive p-type) by the MCZ method.
- rapid heat treatment first heat treatment step
- the surface of the wafer after the heat treatment was polished by about 5 ⁇ m and etched using a magnetron RIE apparatus (Centura manufactured by Applied Materials). Thereafter, the residual protrusions after etching were measured with a laser scattering type foreign substance inspection apparatus (SP1 manufactured by KLA-Tencor), and the defect density was calculated. The results are shown in Table 2.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
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Abstract
Description
ところで、CZ法で育成されたシリコン単結晶には、通常10-20ppma(JEIDA:日本電子工業振興協会による換算係数を使用)程度の酸素が石英ルツボから溶け出し、シリコン融液界面にてシリコン結晶中に取り込まれる。
一般に、単結晶内の温度分布はCZ炉内構造(以下、ホットゾーン(HZ)という)に依存しており、引き上げ速度を変えてもその分布は殆ど変わらない。このため、同一構造のCZ炉の場合は、V/Gは引き上げ速度の変化のみに対応することになる。即ち、引き上げ速度VとV/Gは近似的には正比例の関係がある。したがって、図4の縦軸には引き上げ速度Vを用いている。
また、成長速度を遅くしていくと、結晶周辺部に発生していたOSFリングが結晶内部に向かって収縮していき、ついには消滅する。更に成長速度を遅くすると、Vaやインタースティシャルシリコンの過不足が少ないニュートラル(Neutral:以下Nという)領域が出現する。このN領域はVaやIの偏りはあるが飽和濃度以下であるため、凝集して欠陥とはならないことが判明してきた。このN領域は、Vaが優勢なNv領域とIが優勢なNi領域に分別される。
これらのことから、結晶の中心から径方向全域に渡ってN領域となるような範囲に成長速度を制御しながら引き上げた単結晶を切断、研磨することにより、全面がN領域の極めて欠陥の少ないシリコン基板を得ることができる。
RTP処理後に酸素析出熱処理を行うことによって、BMDが形成されるメカニズムについては、特許文献1や特許文献2に詳細に記述されている。ここで、BMD形成メカニズムについて簡単に説明する。
このようなRTP処理の場合は極めて短時間アニールであるため、酸素の外方拡散が殆ど発生せず、表層での酸素濃度の低下は無視できる。
この方法の場合は、材料となるSi中にグローイン欠陥が存在しないため、RTP処理により容易に無欠陥とすることができるように考えられるが、全面がN領域のシリコン基板を準備し、RTP処理を行った後、酸化膜の長期信頼性である経時破壊特性であるTDDB特性を測定すると、シリコン基板のNv領域においてTZDB特性は殆ど低下しないが、TDDB特性が低下する場合がある。特許文献5に記載したように、このTDDB特性が低下する領域は、Nv領域でかつRIE法で検出される欠陥が存在する領域であることから、表層にRIE欠陥が存在しないシリコン基板及びその製造方法の開発は極めて重要である。
RIE法とは、半導体単結晶基板中の酸化珪素(以下SiOxという)を含有する微小な結晶欠陥を深さ方向の分解能を付与しつつ評価する方法で、特許文献6に開示された方法が知られている。
SiOxを含有する結晶欠陥の形成領域と、含有しない非形成領域とでは、エッチング速度が相違するので(前者の方がエッチング速度が小さい)、上記反応性イオンエッチングを施すと、基板の主表面にはSiOxを含有する結晶欠陥を頂点とした円錐状のヒロックが残留する。結晶欠陥が異方性エッチングによる突起部の形で強調され、微小な欠陥であっても容易に検出することができる。
熱処理によって、シリコン基板中に過飽和に溶存していた酸素がSiOxとして析出した酸素析出物が形成される。そして、このシリコン基板を、市販のRIE装置を用いて、ハロゲン系混合ガス(例えばHBr/Cl2/He+O2)雰囲気中で、シリコン基板内に含まれるBMDに対して高選択比の異方性エッチングによってシリコン基板の主表面からエッチングすると、BMDに起因した円錐状突起物がエッチング残渣(ヒロック)として形成される。したがって、このヒロックに基づいて結晶欠陥を評価することができる。例えば、得られたヒロックの数を数えれば、エッチングした範囲のシリコン基板中のBMDの密度を求めることができる。
このように、第2熱処理工程において、上記の急速熱処理を施すことによって、シリコン基板内部の空孔濃度を効率的に低下させ、空孔起因の欠陥の発生を効果的に抑制することができるため、ライフタイムの低下を確実に防止できる。
このような第2熱処理工程を行うことで、空孔濃度の低減や空孔起因の欠陥の発生抑制を十分に達成でき、確実にライフタイムの低下の無いシリコン基板を製造することができる。また、希ガス及び窒化膜形成雰囲気ガスのうちの少なくとも一種類のガスを含む雰囲気であれば、デバイス作製工程で十分なBMDが析出するシリコン基板とすることができる。
このような第2熱処理工程を行うことで、空孔濃度の低減や空孔起因の欠陥の発生抑制を十分に達成でき、確実にライフタイムの低下の無いシリコン基板とすることができる。また、第2の雰囲気が還元性ガス又は還元性ガスと希ガスの混合ガスの雰囲気の場合には、温度が900℃未満であればスリップ転位の発生も確実に防止することができ、BMD析出も良好なシリコン基板を製造できる。
このような第2熱処理工程を行うことで、格子間シリコンの注入による空孔の消滅や空孔起因の欠陥抑制を十分に達成でき、よりライフタイムの長いシリコン基板とすることができる。
このようなシリコン単結晶ウェーハとすることで、第1の熱処理工程で、より欠陥を消滅させ易いため、後工程で研磨、エッチング等を行っても、デバイス作製領域となる表面に欠陥が表出せず、より高品質のシリコン基板を製造することができる。
このようなシリコン基板であれば、デバイス作製領域の欠陥やライフタイムの低下によるデバイス特性不良が無く、高品質のデバイス作製用基板となる。
その結果、1300℃より高い温度で急速熱処理を施すことによって、シリコン基板の表面から少なくとも1μmの深さまでRIE法により検出される欠陥を消滅させることができることを見出した。
図1は、シリコン単結晶引き上げ装置を示す概略図である。図2は、枚葉式の急速加熱・急速冷却装置を示す概略図である。
育成するシリコン単結晶インゴットの直径等は特に限定されず、例えば150mm~300mm、あるいはそれ以上とすることができ、用途に合わせて所望の大きさに育成することができる。
COP等が発生しやすい、V-Rich領域を含むシリコン単結晶インゴットから切り出されたシリコン基板であっても、本発明であれば、欠陥を大きく低減できる。また、全面がOSF領域、全面がN領域、OSF領域及びN領域が混合した領域のいずれかであるシリコン単結晶インゴットから切り出されたシリコン基板であれば、最も消滅しにくいCOPをほとんど含まないため、本発明の急速熱処理によって確実に欠陥を消滅させることができ、また、より深い位置のRIE欠陥も消滅させることが容易であるため、特に有効である。
図1に単結晶引き上げ装置10を示す。この単結晶引き上げ装置10は、引き上げ室11と、引き上げ室11中に設けられたルツボ12と、ルツボ12の周囲に配置されたヒータ14と、ルツボ12を回転させるルツボ保持軸13及びその回転機構(図示せず)と、シリコンの種結晶を保持するシードチャック21と、シードチャック21を引き上げるワイヤ19と、ワイヤ19を回転または巻き取る、巻き取り機構(図示せず)とを備えて構成されている。ルツボ12は、その内側のシリコン融液(湯)18を収容する側には石英ルツボが設けられ、その外側には黒鉛ルツボが設けられている。また、ヒータ14の外側周囲には断熱材15が配置されている。
また、引き上げ室11の水平方向の外側に、磁石(図示せず)を設置し、シリコン融液18に水平方向あるいは垂直方向の磁場を印加することによって、融液の対流を抑制し、単結晶の安定成長を図る、いわゆるMCZ法の装置を用いることもできる。
これらの装置の各部は、例えば従来と同様のものとすることができる。
まず、ルツボ12内で、シリコンの高純度多結晶原料を融点(約1420℃)以上に加熱して融解する。次に、ワイヤ19を巻き出すことにより、シリコン融液18の表面略中心部に種結晶の先端を接触または浸漬させる。その後、ルツボ保持軸13を適宜の方向に回転させるとともに、ワイヤ19を回転させながら巻き取り、種結晶を引き上げることにより、シリコン単結晶インゴット20の育成を開始する。
以後、引き上げ速度と温度を所望の欠陥領域となるように適切に調整し、略円柱形状のシリコン単結晶インゴット20を得る。
この第1熱処理工程で、1300℃より高い熱処理温度であれば、シリコン基板の表面から少なくとも深さ1μmの領域のRIE欠陥を確実に消滅させることができ、欠陥がデバイス作製領域となる表面に現れることが無く、デバイス不良を防止することができる。
また、上記の雰囲気であれば、基板表層のRIE欠陥を消滅させると同時に、基板内部に新たな空孔等の点欠陥を均一に形成することができ、後工程のデバイス熱処理時等にBMD形成が大幅に促進され、ゲッタリング能力の高いシリコン基板を製造することができる。また、酸化性ガスを含む雰囲気の場合には、濃度によってはデバイス熱処理時のBMD形成が抑制される。このように、雰囲気を調節して、デバイス熱処理時のBMD形成を制御することができる。
この急速加熱・急速冷却装置52は、石英からなるチャンバー53を有し、このチャンバー53内でシリコン基板Wを急速熱処理できるようになっている。加熱は、チャンバー53を上下左右から囲繞するように配置される加熱ランプ54(例えばハロゲンランプ)によって行う。この加熱ランプ54は、それぞれ独立に供給される電力を制御できるようになっている。
そして、シリコン基板Wは、石英トレイ56に形成された3点支持部57上に配置される。石英トレイ56のガス導入口側には、石英製のバッファ58が設けられており、酸化性ガスや窒化性ガス、Arガス等の導入ガスが、シリコン基板Wに直接当たるのを防ぐことができる。
このような、第2熱処理工程により、空孔の凝集や空孔に起因した欠陥準位が形成されるのを抑制し、ライフタイムが大きく低下することを防ぐことができるため、熱処理後のライフタイムが500μsec以上のシリコン基板を得ることができる。
上記の条件で第2熱処理工程を行えば、空孔濃度の低減や、空孔起因の欠陥準位の形成の抑制を効率的に達成することができ、ライフタイムの低下を効果的に防止することができる。
このような熱処理の雰囲気、温度であれば、空孔の凝集や空孔に起因した欠陥準位の形成をより効果的に抑制することができる。さらに、第2の雰囲気が希ガス及び窒化膜形成雰囲気ガスのうちの少なくとも一種類のガスを含む雰囲気であれば、デバイス熱処理時のBMD形成がより促進される。また、当該雰囲気の際の第2の温度としては、300℃以上900℃以下もしくは1100℃以上1250℃以下が特に好ましい。当該範囲の温度であれば、空孔の凝集をさらに抑制することができ、ライフタイム低下のほとんど無い熱処理を実施できる。
このような熱処理の雰囲気、温度でも、空孔の凝集をより効果的に抑制することができ、空孔や空孔に起因した欠陥準位の形成を確実に抑制することができる。さらに、還元性ガス又は還元性ガスと希ガスの混合ガスの雰囲気であれば、デバイス熱処理時のBMD形成もより促進される。第2の温度が900℃未満であれば、スリップ転位が入りにくいため、好ましい。また、還元性ガスが水素の場合、基板内に水素が注入される。水素は、デバイスプロセスの熱処理によりドナーを形成する原因となり、このようなドナーはライフタイムの低下や基板抵抗率を変化させる原因となる。特に近年、デバイスプロセスの熱処理は低温化が進んでおり、ドナーを形成する原因となる水素がシリコン基板中に高濃度に分布することは好ましくないため、上記300℃以上900℃未満の温度範囲で本発明の第2熱処理工程を行えば、注入される水素は低濃度なので問題とならない。
このような熱処理の雰囲気、温度でも、空孔の凝集をより効果的に抑制することができ、空孔に起因した欠陥準位の形成を確実に抑制することができる。この酸化性ガス雰囲気の場合、700℃より高く1100℃未満の熱処理温度では、空孔の凝集抑制効果が低いが、上記300℃以上700℃以下、もしくは、1100℃以上1300℃未満の温度範囲であれば、効果的に空孔の凝集を抑制して、空孔起因の欠陥を確実に抑制できる。
(実施例、比較例)
図1のシリコン単結晶引き上げ装置により、横磁場を印加して、MCZ法によりN領域のシリコン単結晶インゴット(直径12インチ(300mm)、方位<100>、導電型p型)を育成し、育成したインゴットから切り出した複数のシリコン単結晶ウェーハに、図2の急速加熱・急速冷却装置(ここでは、Mattson社製Helios)を用いて、Arガス雰囲気下、1350℃、10秒間の急速熱処理(第1熱処理工程)を施し、ウェーハ表層のRIE欠陥を消滅させた。
このように作製したウェーハのうち各熱処理条件1枚ずつに、マグネトロンRIE装置(Applied Materials社製 Centura)を用いてエッチングを行った。その後レーザー散乱方式の異物検査装置(KLA-Tencor社製 SP1)でエッチング後の残渣突起を計測し、欠陥密度を算出した結果、いずれのウェーハも第1熱処理工程で欠陥が消滅して、欠陥密度は0であった。
図3に示すように、O2ガス雰囲気以外の雰囲気での急速熱処理を行ったウェーハのBMD密度は全体として高く、一方、O2ガス雰囲気での急速熱処理を行ったウェーハのBMD密度は、BMD形成が抑制され、検出下限以下であった。このように、雰囲気により、デバイス作製熱処理の際のBMD形成を容易に制御することができる。
図1のシリコン単結晶引き上げ装置により、横磁場を印加して、MCZ法によりN領域のシリコン単結晶インゴット(直径12インチ(300mm)、方位<100>、導電型p型)を育成し、育成したインゴットから切り出した複数のシリコン単結晶ウェーハに、図2の急速加熱・急速冷却装置(ここでは、Mattson社製Helios)を用いて、Arガス雰囲気、N2ガス雰囲気、NH3/Arガス雰囲気、O2ガス雰囲気の各雰囲気で、1250~1350℃、10秒間の急速熱処理(第1熱処理工程)を施し、ウェーハ表層のRIE欠陥を消滅させた。
また、別のウェーハのライフタイムを実施例と同様の方法で測定した結果を表3に示す。
Claims (7)
- シリコン基板を製造する方法であって、少なくとも、
チョクラルスキー法により育成したシリコン単結晶インゴットから切り出されたシリコン基板に、急速加熱・急速冷却装置を用いて、窒化膜形成雰囲気ガス、希ガス及び酸化性ガスのうちの少なくとも一種類のガスを含む第1の雰囲気で、1300℃より高くかつシリコン融点以下の第1の温度で1-60秒保持して急速熱処理を施す第1熱処理工程と、該第1熱処理工程に続いて、前記シリコン基板内部の空孔起因の欠陥の発生を抑制する第2の温度及び第2の雰囲気に制御し、前記シリコン基板に前記制御した第2の温度及び第2の雰囲気で急速熱処理を施す第2熱処理工程とを具備することを特徴とするシリコン基板の製造方法。 - 前記第2熱処理工程において、前記第1熱処理工程に続いて、前記第1の温度から5℃/sec以上150℃/sec以下の降温速度で1300℃未満の前記第2の温度まで急速降温し、前記シリコン基板に、前記第2の温度で1-60秒保持して急速熱処理を施すことによって、前記第2熱処理工程を行うことを特徴とする請求項1に記載のシリコン基板の製造方法。
- 前記第2熱処理工程における第2の雰囲気を、希ガス及び窒化膜形成雰囲気ガスのうちの少なくとも一種類のガスを含む雰囲気とし、前記第2の温度を300℃以上1300℃未満とすることを特徴とする請求項1又は請求項2に記載のシリコン基板の製造方法。
- 前記第2熱処理工程における第2の雰囲気を、還元性ガス又は還元性ガスと希ガスの混合ガスの雰囲気とし、前記第2の温度を300℃以上900℃未満とすることを特徴とする請求項1又は請求項2に記載のシリコン基板の製造方法。
- 前記第2熱処理工程における第2の雰囲気を、酸化性ガス雰囲気とし、前記第2の温度を300℃以上700℃以下、もしくは、1100℃以上1300℃未満とすることを特徴とする請求項1又は請求項2に記載のシリコン基板の製造方法。
- 前記シリコン基板を、全面がOSF領域、全面がN領域、OSF領域及びN領域が混合した領域のいずれかであるシリコン単結晶インゴットから切り出されたシリコン単結晶ウェーハとすることを特徴とする請求項1乃至請求項5のいずれか一項に記載のシリコン基板の製造方法。
- 請求項1乃至請求項6のいずれか一項に記載のシリコン基板の製造方法によって製造されたシリコン基板であって、前記シリコン基板のデバイス作製領域となる表面から少なくとも1μmの深さにRIE法により検出される欠陥が存在せず、かつ、前記シリコン基板のライフタイムが500μsec以上であることを特徴とするシリコン基板。
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US10177008B2 (en) * | 2014-01-14 | 2019-01-08 | Sumco Corporation | Silicon wafer and method for manufacturing the same |
JP6044660B2 (ja) * | 2015-02-19 | 2016-12-14 | 信越半導体株式会社 | シリコンウェーハの製造方法 |
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