WO2022158148A1 - エピタキシャルウェーハの製造方法 - Google Patents

エピタキシャルウェーハの製造方法 Download PDF

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WO2022158148A1
WO2022158148A1 PCT/JP2021/044763 JP2021044763W WO2022158148A1 WO 2022158148 A1 WO2022158148 A1 WO 2022158148A1 JP 2021044763 W JP2021044763 W JP 2021044763W WO 2022158148 A1 WO2022158148 A1 WO 2022158148A1
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Prior art keywords
single crystal
crystal silicon
oxygen
layer
epitaxial
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French (fr)
Japanese (ja)
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克佳 鈴木
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Shin Etsu Handotai Co Ltd
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Shin Etsu Handotai Co Ltd
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Priority to KR1020237023432A priority Critical patent/KR20230132455A/ko
Priority to US18/269,646 priority patent/US20240063027A1/en
Priority to JP2022552294A priority patent/JP7231120B2/ja
Priority to CN202180088195.8A priority patent/CN116685723A/zh
Priority to EP21921250.3A priority patent/EP4283024A4/en
Publication of WO2022158148A1 publication Critical patent/WO2022158148A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
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    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/22—Sandwich processes
    • 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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    • 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
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    • 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
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    • 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
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    • H01L21/02595—Microstructure polycrystalline

Definitions

  • the present invention relates to an epitaxial wafer manufacturing method.
  • Silicon substrates that form semiconductor devices such as solid-state imaging devices and other transistors are required to have the function of gettering elements that disrupt device characteristics, such as heavy metals.
  • a polycrystalline silicon (Poly-Si) layer is provided on the back surface of the silicon substrate, a method is used to form a layer damaged by blasting, a silicon substrate with a high concentration of boron is used, or a deposition method is used.
  • Various methods have been proposed and put into practical use, such as forming objects.
  • a metal with a high ionization tendency low electronegativity
  • proximity gettering in which a gettering layer is formed near the active region of an element, has also been proposed.
  • a substrate in which silicon is epitaxially grown on a substrate into which carbon ions are implanted.
  • the element In gettering, the element must diffuse to the gettering site (the energy of the entire system is lowered by bonding or clustering at the site rather than when the metal exists as a single element).
  • proximity gettering methods have been proposed. .
  • oxygen can be used for proximity gettering, it is thought that a silicon substrate with a very effective gettering layer will be obtained.
  • the epitaxial wafer has an oxygen atomic layer in the middle of the epitaxial layer, metal impurities can be gettered reliably even in recent low-temperature processes.
  • the above has focused on gettering metal impurities, but for example, it is known that the effect of oxygen is to prevent autodoping during epitaxial growth by forming a CVD oxide film on the back surface.
  • Patent Document 1 describes a method of forming a thin layer of oxygen on silicon and then growing silicon as a structure. This method is a technique based on ALD (“atomic layer deposition”). ALD is a method of adsorbing a molecule containing a target atom and then dissociating/desorbing unnecessary atoms (molecules) in the molecule. Yes, and widely used.
  • ALD atomic layer deposition
  • Patent Document 2 describes a method of forming a natural oxide film on a silicon clean surface formed by vacuum heating or the like, and then adsorbing and depositing an oxide film or another substance.
  • Patent Documents 3 and 4 show that it is possible to improve device characteristics (mobility) by introducing a plurality of oxygen atomic layers into a silicon substrate.
  • Patent Document 5 shows a method of forming an epitaxial layer using SiH4 gas on an atomic layer with a thickness of 5 nm or less. Also, a method of forming an oxygen atomic layer with oxygen gas is shown as the atomic layer.
  • Patent Documents 6 and 7 describe a method of epitaxially growing single crystal silicon after forming an oxide film by bringing the surface of a semiconductor substrate into contact with an oxidizing gas or an oxidizing solution.
  • Patent Document 6 describes a method of flowing silicon film forming gas after flowing oxidizing gas.
  • Non-Patent Document 1 shows a method of forming an amorphous silicon film by low-pressure CVD after removing a native oxide film with HF, oxidizing it in the atmosphere, and then forming single crystal silicon by heat treatment for crystallization.
  • the method of gettering metal impurities by forming an oxygen layer in the wafer has been conventionally used.
  • the conventional technique although a thin layer of oxygen can be obtained with high accuracy, there are problems in that the structure of the apparatus is complicated and the number of steps is increased.
  • Patent Document 1 cannot epitaxially grow single crystal silicon by ALD, so there is a problem that at least two chambers for ALD and CVD are required, which complicates the configuration of the apparatus. Moreover, since the oxidation is performed with ozone, there is a problem that a special generator for generating ozone is required.
  • Patent Document 5 there is a problem that it is necessary to prepare two chambers with separate exhaust systems in order to prevent SiH 4 from reacting with oxygen and causing an explosion.
  • Non-Patent Document 1 In the method described in Non-Patent Document 1, it was necessary to perform heat treatment during crystallization, and there was a problem that the number of process steps increased. In addition, since amorphous silicon generally contains a large amount of hydrogen, defects caused by hydrogen may be formed during heat treatment for crystallization.
  • the conventional technology has the problem that there is no knowledge for stably introducing an oxygen layer and no specific knowledge for forming an epitaxial layer of high-quality single crystal silicon.
  • Patent Document 2 does not describe at all a method for forming an epitaxial layer of single crystal silicon on a wafer surface without generating dislocations and stacking faults.
  • Patent Documents 3 and 4 do not mention a specific method for growing a silicon wafer into which multiple oxygen atomic layers are introduced.
  • Patent Document 7 does not describe a method for removing the native oxide film before contact with an oxidizing gas or an oxidizing solution.
  • the present invention has been made to solve the above-described problems of the prior art, and is capable of stably and easily introducing an oxygen atomic layer into an epitaxial layer and producing an epitaxial layer of high-quality single crystal silicon. It aims at providing the manufacturing method of the epitaxial wafer which has.
  • the present invention has been made to achieve the above objects, and is a method for producing an epitaxial wafer for forming a single crystal silicon layer on a single crystal silicon wafer, wherein hydrofluoric acid is applied to the surface of the single crystal silicon wafer. removing an oxide film; forming an oxygen atomic layer on the surface of the single crystal silicon wafer from which the natural oxide film has been removed; and forming the oxygen atomic layer on the surface of the single crystal silicon wafer.
  • a method for producing an epitaxial wafer comprising the step of epitaxially growing a layer, wherein the planar concentration of oxygen in the oxygen atomic layer is 1 ⁇ 10 15 atoms/cm 2 or less.
  • single crystal silicon can be grown without forming dislocations and stacking faults on the oxygen atomic layer while leaving the oxygen atomic layer.
  • the oxygen atoms are removed by rinsing the single crystal silicon wafer with pure water and/or leaving the single crystal silicon wafer in an atmosphere containing oxygen. It can be a method of manufacturing an epitaxial wafer for forming layers.
  • an oxygen atomic layer having a desired planar oxygen concentration can be easily formed in a short time.
  • the oxygen concentration of the oxygen atomic layer can be controlled by leaving the single crystal silicon wafer in an atmosphere containing oxygen.
  • the oxygen concentration of the oxygen atomic layer can be controlled in a short period of time.
  • the epitaxial wafer manufacturing method can be such that epitaxial growth is performed at a temperature of 450°C or higher and 800°C or lower.
  • epitaxial growth temperature within such a temperature range, epitaxial growth can be performed more stably without causing defects.
  • the process of forming the oxygen atomic layer and the process of epitaxially growing the single-crystal silicon may be alternately performed multiple times to produce an epitaxial wafer.
  • An epitaxial wafer manufactured by the epitaxial wafer manufacturing method according to the present invention can be provided with a gettering layer in the vicinity of the device region.
  • the epitaxial wafer manufacturing method of the present invention it is possible to provide a method for stably introducing an oxygen atomic layer into the epitaxial layer in a silicon epitaxial wafer employed in advanced devices.
  • FIG. 1 is transmission electron microscope images of cross sections of silicon epitaxial wafers in Example 1 and Comparative Example 1.
  • FIG. 4 is a transmission electron microscope image of a cross section of a silicon epitaxial wafer in Example 2.
  • the present inventors have found a method for producing an epitaxial wafer in which a single crystal silicon layer is formed on a single crystal silicon wafer, wherein the surface of the single crystal silicon wafer is naturally oxidized with hydrofluoric acid.
  • FIG. 2 is a diagram showing an epitaxial wafer obtained by the epitaxial wafer manufacturing method of the present invention.
  • An epitaxial wafer 10A according to the present invention has a single crystal silicon layer 3 on a single crystal silicon wafer 1 and an oxygen atomic layer 2 between the single crystal silicon layer 3 and the single crystal silicon wafer 1 .
  • the planar concentration of oxygen in the oxygen atomic layer 2 of the epitaxial wafer 10A according to the present invention is 1 ⁇ 10 15 atoms/cm 2 or less.
  • An epitaxial wafer having an oxygen atomic layer with a planar concentration of oxygen within such a range will have few stacking faults and dislocations in the epitaxially grown single crystal silicon layer and will have high crystallinity.
  • the lower limit of the planar concentration of oxygen is not limited, and may be greater than zero.
  • it is preferably 1 ⁇ 10 13 atoms/cm 2 or more.
  • the single crystal silicon wafer 1 may be manufactured in any manner.
  • a CZ wafer manufactured by the Czochralski method (hereinafter referred to as the "CZ method") may be used, or an FZ wafer manufactured by the floating zone method (hereinafter referred to as the "FZ method") Wafers may also be used.
  • an epitaxial wafer obtained by epitaxially growing single crystal silicon on a single crystal silicon wafer manufactured by the CZ method or the FZ method may be used.
  • FIG. 3 is a diagram showing an epitaxial wafer 10B in which a plurality of oxygen atomic layers and single crystal silicon layers are alternately laminated on a single crystal silicon wafer.
  • an epitaxial wafer in which an oxygen atomic layer 2 and a single crystal silicon layer 3 are alternately and repeatedly laminated on a single crystal silicon wafer 1 can be obtained by the epitaxial wafer manufacturing method of the present invention.
  • the uppermost surface at this time is a single crystal silicon layer.
  • FIG. 1 shows a production flow of an epitaxial wafer according to the present invention.
  • the step of S11 in FIG. 1 is a step of preparing a single crystal silicon wafer.
  • the manufacturing method of the single crystal silicon wafer used as the substrate is not particularly limited.
  • a single crystal silicon wafer manufactured by the CZ method or a single crystal silicon wafer manufactured by the FZ method may be used.
  • an epitaxial wafer obtained by epitaxially growing single crystal silicon on a single crystal silicon wafer manufactured by the CZ method or the FZ method may be used.
  • the process of S12 in FIG. 1 is a process of removing the native oxide film with hydrofluoric acid (hydrofluoric acid).
  • hydrofluoric acid hydrofluoric acid
  • the chemical solution used may be hydrofluoric acid alone or a chemical solution containing other components such as buffered hydrofluoric acid.
  • the concentration of hydrofluoric acid is sufficient as long as it can remove the native oxide film, and can be, for example, 0.001% or more and 60% or less.
  • the temperature of hydrofluoric acid can be 10° C. or higher and 50° C. or lower. If the temperature is 10° C. or higher, the occurrence of dew condensation on the wafer after hydrofluoric acid treatment can be more effectively suppressed. Further, if the temperature is 50° C. or less, the amount of volatilized hydrofluoric acid can be set within an appropriate range, so safety can be enhanced.
  • the removal treatment (washing) of the natural oxide film with hydrofluoric acid can be performed until the water repellency can be confirmed, but it can be, for example, 1 second or more and 1 hour or less. If the time is 1 second or more, the native oxide film can be removed more reliably. Moreover, productivity can be maintained by making it 1 hour or less.
  • batch-type cleaning equipment may be used, or single-wafer cleaning equipment may be used.
  • the oxide film may be removed using hydrofluoric acid vapor.
  • the step S13 in FIG. 1 is a step of forming an oxygen atomic layer on the surface of the single crystal silicon wafer from which the natural oxide film has been removed.
  • oxygen atoms are stable at the bond center position between a silicon atom and the nearest silicon atom. ⁇ 10 15 atoms/cm 2 . If the planar concentration of oxygen is 1 ⁇ 10 15 atoms/cm 2 , this corresponds to 0.74 atomic layers.
  • the method of forming the oxygen atomic layer is not particularly limited.
  • an oxygen atomic layer can be formed by rinsing with pure water after removing the natural oxide film. By using pure water, an oxygen atomic layer can be formed in a short time.
  • the temperature of the pure water can be 10°C or higher and 100°C or lower. If the temperature is 10° C. or higher, it is possible to more effectively suppress dew condensation on the wafer after rinsing with pure water. Also, the temperature can be 100° C. or lower, which is the boiling point of water.
  • the time for rinsing with pure water can be 1 second or more and 1 hour or less. If the time is 1 second or longer, the oxygen atomic layer can be formed more reliably. In addition, it is possible to prevent it from taking too much time by making it 1 hour or less.
  • a batch-type cleaning device For pure water rinsing, either a batch-type cleaning device or a single-wafer cleaning device may be used.
  • Drying after rinsing may be performed in the air or in an inert gas atmosphere. According to studies by the present inventors, the epitaxial growth of single crystal silicon is more stable by sufficiently reducing the amount of organic matter in the atmosphere.
  • An oxygen atomic layer can also be formed by leaving the wafer in an atmosphere containing oxygen after removing the natural oxide film.
  • the oxygen concentration of the oxygen atomic layer can be accurately controlled by leaving in an oxygen-containing atmosphere. Since the surface of the silicon substrate after removing the native oxide film with hydrofluoric acid is terminated with hydrogen, it is not easily oxidized even in an oxygen atmosphere. The oxygen concentration of the oxygen atomic layer can be controlled by the standing time and temperature. Since oxidation proceeds even at room temperature, it is not necessary to place the substrate in a heat treatment furnace for oxidation. In order to prevent defects from occurring during epitaxial growth due to particles adhering to the single crystal silicon wafer, it is desirable that the environment in which the wafer is left is in a clean room.
  • the oxygen atomic layer can be formed by combining the treatment of rinsing with pure water after removing the natural oxide film and the treatment of leaving the wafer in an atmosphere containing oxygen.
  • the oxygen concentration of the oxygen atomic layer can be controlled in a short period of time with high accuracy.
  • S14 in FIG. 1 is a step of epitaxially growing single crystal silicon.
  • Monosilane or disilane can be used as the gas used for growth.
  • Nitrogen or hydrogen may be used as a carrier gas.
  • the pressure of the chamber for epitaxial growth may be any pressure that does not generate micro silicon crystals in the gas phase.
  • the pressure can be 133 Pa or more and 13300 Pa or less.
  • a batch type may be used, or a single wafer type may be used.
  • epitaxial growth of single crystal silicon can be performed at a temperature of 450°C or higher and 800°C or lower. Growth at such a temperature can prevent the formation of dislocations and stacking faults in the epitaxial layer. Since the higher the temperature, the higher the epitaxial growth rate, film formation at a high temperature makes it possible to form a thick epitaxial layer in a short time. On the other hand, if it is desired to form a thin epitaxial layer, the film should be formed at a low temperature. Thus, the growth temperature can be varied according to the desired thickness of the epitaxial layer. Also, the deposition time can be adjusted to adjust the thickness of the epitaxial layer.
  • hydrogen baking is usually performed immediately before epitaxial growth to remove a natural oxide film on the surface of the substrate and to clean the epitaxial growth. It is preferable to start the epitaxial growth when the predetermined growth temperature is reached without performing the This is to prevent the disappearance of the oxygen atomic layer.
  • the term "hydrogen baking" as used herein means holding a single crystal silicon wafer at 800° C. or higher in a hydrogen atmosphere for a certain period of time. Since the oxygen atomic layer does not disappear at temperatures below 800° C., there is no problem in flowing hydrogen as a carrier gas before epitaxial growth at temperatures below 800° C.
  • the planar concentration of oxygen in the oxygen atomic layer By setting the planar concentration of oxygen in the oxygen atomic layer to 1 ⁇ 10 15 atoms/cm 2 or less, defects are not formed in the epitaxial layer. This is because the crystallinity of the substrate is maintained when the amount of oxidation is small. Therefore, there is no lower limit for the plane concentration of oxygen, and it is sufficient that it is greater than zero. When the amount of oxidation is large and the plane concentration of oxygen in the oxygen atomic layer is higher than 1 ⁇ 10 15 atoms/cm 2 , an epitaxial layer with high crystallinity is not formed and becomes polycrystalline silicon or amorphous silicon.
  • the planar concentration of oxygen can be measured, for example, by SIMS (Secondary Ion Mass Spectrometry).
  • SIMS Secondary Ion Mass Spectrometry
  • an oxygen peak is formed at the depth where the oxide layer is formed.
  • the planar concentration can be obtained by accumulating the product of the volume concentration and the depth due to one sputtering in the vicinity of the peak.
  • the step of forming an oxygen atomic layer on the surface of the single crystal silicon wafer and the step of epitaxially growing the single crystal silicon can be alternately performed multiple times.
  • the gettering effect can be enhanced as compared with the case of a single layer.
  • Example 1 Comparative Example 1
  • the conductivity type, diameter, and crystal plane orientation of the prepared single crystal silicon substrate are as follows.
  • Example 1 had a planar oxygen concentration of 5 ⁇ 10 14 atoms/cm 2 and 1 ⁇ 10 15 atoms/cm 2
  • Comparative Example 1 had a planar oxygen concentration of 2 ⁇ 10 15 atoms/cm 2 . cm 2 was found to be obtained.
  • Example 2 The same single crystal silicon substrates as in Example 1 and Comparative Example 1 were prepared. Next, in order to remove a native oxide film from the prepared single crystal silicon substrate, the substrate was cleaned with hydrofluoric acid using a batch or single wafer system, and then rinsed with pure water. After that, an oxygen atomic layer was formed so that the exposure time in the atmosphere of cleanliness class 100 was within 10 minutes, and then epitaxial growth of single crystal silicon was performed without hydrogen baking. At this time, the pressure was 4000 Pa and the growth temperature was 580°C.
  • planar concentration of oxygen in the oxygen atomic layer was measured by SIMS.
  • the planar concentration of oxygen in the oxygen atomic layer was 1 ⁇ 10 14 atoms/cm 2 in both hydrofluoric acid cleaning methods.
  • an oxygen atomic layer can be stably and easily introduced into the epitaxial layer, and an epitaxial wafer having an epitaxial layer of high-quality single crystal silicon can be obtained. Become.
  • the present invention is not limited to the above embodiments.
  • the above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of

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WO2025041540A1 (ja) * 2023-08-22 2025-02-27 信越半導体株式会社 エピタキシャルウェーハの製造方法

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