WO2018230301A1 - Epitaxial wafer production method - Google Patents

Epitaxial wafer production method Download PDF

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Publication number
WO2018230301A1
WO2018230301A1 PCT/JP2018/020091 JP2018020091W WO2018230301A1 WO 2018230301 A1 WO2018230301 A1 WO 2018230301A1 JP 2018020091 W JP2018020091 W JP 2018020091W WO 2018230301 A1 WO2018230301 A1 WO 2018230301A1
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layer
gas
epitaxial
atomic layer
oxygen
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PCT/JP2018/020091
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French (fr)
Japanese (ja)
Inventor
大槻　剛
康 水澤
鈴木　克佳
石崎　順也
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信越半導体株式会社
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Priority to KR1020197031426A priority Critical patent/KR102482578B1/en
Priority to CN201880034863.7A priority patent/CN110678964A/en
Publication of WO2018230301A1 publication Critical patent/WO2018230301A1/en

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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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Definitions

  • the present invention relates to a method for manufacturing an epitaxial wafer.
  • a silicon substrate on which a semiconductor element such as a solid-state imaging element or other transistor is formed is required to have a function of gettering elements that detract from element characteristics such as heavy metals.
  • gettering there is a method of forming a polycrystalline silicon (Poly-Si) layer on the back of the silicon substrate, forming a layer damaged by blasting, utilizing the high-concentration boron of the silicon substrate, Various methods have been proposed and put into practical use. In gettering by oxygen precipitation, gettering is performed by incorporating a metal having a large ionization tendency (small electronegativity) with respect to oxygen having a large electronegativity.
  • proximity gettering in which a gettering layer is formed in the vicinity of the active region of the element has been proposed.
  • a substrate obtained by epitaxially growing silicon on a substrate into which carbon is ion-implanted.
  • the element needs to diffuse to the gettering site (the energy of the entire system is reduced by bonding or clustering at the site rather than the metal being present as a single element).
  • Proximity gettering methods have been proposed in consideration of the fact that the diffusion coefficient of metal elements contained in silicon varies from element to element, and that metals cannot diffuse to the gettering site due to recent process low temperatures.
  • oxygen can be used for proximity gettering
  • a silicon substrate having a very powerful gettering layer is considered.
  • an epitaxial wafer having an oxygen atomic layer in the middle of an epitaxial layer can reliably getter metal impurities even in recent low-temperature processes.
  • the gettering of metal impurities has been mainly described.
  • an effect of oxygen an effect of preventing autodoping during epitaxial growth is known by forming a CVD oxide film on the back surface.
  • group IV group 14
  • gettering effect due to carbon application to optical devices in combination with silicon oxide film in Ge, Sn grows Ge etc. on silicon
  • other than group IV, other than group IV various effects of combinations of silicon and other elements such as improvement of strength by promoting precipitation are expected and applied in nitrogen.
  • Patent Document 1 is a method of forming a thin layer of oxygen on silicon and further growing silicon. This method is based on ALD (“Atomic layer deposition”, “Atomic layer deposition method”).
  • ALD is a method to adsorb molecules containing target atoms and then dissociate and desorb unnecessary atoms (molecules) in the molecule. It uses surface bonding, has high accuracy, has good reaction controllability, and is widely used. Although it is used, there is a weak point that impurities that are unnecessary and unintentional for forming an atomic layer are generated by eliminating unnecessary molecules. Actually, since the ALD method uses molecules containing carbon to form an oxygen layer, there is a concern about the influence of carbon (unnecessary carbon).
  • Patent Document 2 is a technology related to a reactor for realizing a substrate similar to that of Patent Document 1, but this assumes MOVPE (metal organic chemical vapor deposition) as a source gas / method.
  • MOVPE metal organic chemical vapor deposition
  • An organic metal is used to be MOVPE.
  • reaction control is easy, there is a concern of unnecessary impurity metals when forming the oxygen atomic layer. In particular, there is a concern about metal contamination when applied to the silicon substrate itself.
  • Patent Documents 1 and 2 are performed based on respective techniques of ALD or MOVPE.
  • Patent Documents 3 and 4 show that by introducing a plurality of oxygen atom layers into a silicon substrate, device characteristics (mobility) can be improved, but no specific growth method is mentioned. Absent.
  • Patent Document 5 describes delta doping, which is disclosed as a basic technique for embedding a dopant in a linear shape, but it is considered difficult to spread the entire surface of the wafer.
  • an object of the present invention is to provide an epitaxial wafer manufacturing method capable of stably introducing an atomic layer such as oxygen into an epitaxial layer.
  • the present invention provides an epitaxial wafer manufacturing method for forming an epitaxial layer on a silicon substrate, wherein oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus are contained in the epitaxial layer.
  • An epitaxial wafer manufacturing method is provided.
  • an atomic layer made of atoms of elements such as oxygen can be stably formed in the epitaxial layer.
  • the formation of an epitaxial layer in contact with an atomic layer made of atoms of elements such as oxygen is performed using SiH 4 gas having no chlorine atom in the molecule, etching of the atomic layer such as oxygen can be prevented.
  • the atomic layer can be formed as a single atomic layer.
  • an atomic layer of oxygen or the like can be formed as a single atomic layer as described above. Even when such a single atomic layer is formed, the single atomic layer can be stably formed by the method of the present invention.
  • a region in contact with the atomic layer and at least 5 nm from the atomic layer is formed using SiH 4 gas.
  • the atomic layer such as oxygen is formed more stably. be able to.
  • a plurality of the atomic layers can be formed in the epitaxial layer.
  • a plurality of atomic layers such as oxygen can be formed in the epitaxial layer. Moreover, such a structure can be formed stably.
  • a region other than a region formed using the SiH 4 gas among the regions of the epitaxial layer is formed using a SiH 2 Cl 2 gas or a SiHCl 3 gas.
  • the epitaxial layer by forming with SiH 2 Cl 2 gas or SiHCl 3 gas other than the region formed by using a SiH 4 gas, the epitaxial layer in areas away from the atoms of oxygen, such as layer It can be formed thick. As a result, the entire epitaxial layer can be formed in a shorter time, which contributes to productivity and cost.
  • the atomic layer is formed by oxygen gas when forming an oxygen atomic layer, CH 4 gas when forming a carbon atomic layer, NH 3 gas when forming a nitrogen atomic layer, and a germanium atomic layer.
  • oxygen gas when forming an oxygen atomic layer
  • CH 4 gas when forming a carbon atomic layer
  • NH 3 gas when forming a nitrogen atomic layer
  • germanium atomic layer is formed by oxygen gas when forming an oxygen atomic layer
  • an organometallic gas containing Ge is formed
  • an organometallic gas containing Sn is formed when a tin atomic layer is formed
  • B 2 H 6 gas is formed when a boron atomic layer is formed
  • a phosphorus atomic layer is formed.
  • PH 3 gas can be used.
  • An atomic layer such as oxygen can be formed by using these gases.
  • an atomic layer such as oxygen can be stably introduced into the epitaxial layer in the silicon epitaxial wafer employed in the advanced device.
  • a proximity gettering substrate having a proximity gettering effect by an oxygen atomic layer and a functional substrate having a composite function using a group IV element, nitrogen, a dopant, and the like.
  • the present invention is an epitaxial wafer manufacturing method for forming an epitaxial layer on a silicon substrate.
  • one element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus is used.
  • the epitaxial layer in contact with the atomic layer is further formed using SiH 4 gas.
  • an atomic layer formed of atoms of one element among oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus formed in the epitaxial layer is simply referred to as “atomic layer”.
  • FIG. 1 shows a schematic cross-sectional view of an epitaxial wafer 100 having an oxygen atomic layer, which can be manufactured by the epitaxial wafer manufacturing method of the present invention.
  • an epitaxial layer 50 is formed on a silicon substrate 10, and an atomic layer (oxygen atomic layer) 31 made of oxygen atoms and having a thickness of 5 nm or less is formed in the epitaxial layer 50.
  • a silicon epitaxial layer 21 made of silicon is formed between the silicon substrate 10 and the oxygen atomic layer 31.
  • An oxygen atomic layer 31 is formed on the silicon epitaxial layer 21, and a silicon epitaxial layer 22 is formed on the oxygen atomic layer 31.
  • an epitaxial layer 50 including a silicon epitaxial layer 21, an oxygen atom layer 31, and a silicon epitaxial layer 22 is formed.
  • the manufacturing method for forming the oxygen atomic layer 31 is as follows. Epitaxial growth is performed on the silicon substrate 10 to first form a silicon epitaxial layer 21. An oxygen atomic layer 31 is grown on the silicon epitaxial layer 21. Further, silicon is epitaxially grown on the oxygen atom layer 31 to form the silicon epitaxial layer 22. Thereby, the entire epitaxial layer 50 having the oxygen atomic layer 31 is formed, and the epitaxial wafer 100 is formed.
  • FIG. 1 there is one oxygen atom layer, but it is also possible to repeat the oxygen atom layer and silicon epitaxial growth to form a plurality of oxygen atom layers.
  • An epitaxial wafer having a plurality of oxygen atom layers formed in the epitaxial layer is shown in FIG. That is, when the epitaxial wafer 200 shown in FIG. 2 is manufactured, it can be manufactured as follows. First, the silicon epitaxial layer 21 is formed on the silicon substrate 10. An oxygen atom layer 31 is formed on the silicon epitaxial layer 21. Further, the silicon epitaxial layer 22 is formed on the oxygen atom layer 31. The process up to this point is the same as that of FIG. 1, but in the aspect of FIG.
  • the oxygen atom layer 32, silicon epitaxial layer 23, oxygen atom layer 33, silicon epitaxial layer 24, oxygen atom layer 34, silicon epitaxial layer 25 are further provided.
  • an oxygen atom layer 35 and a silicon epitaxial layer 26 are formed.
  • the epitaxial layer 60 in which the structure 40 in which five sets of the silicon epitaxial layer and the oxygen atom layer are repeated is formed can be formed.
  • an epitaxial wafer having a better gettering effect can be obtained.
  • it is sufficient that the oxygen atom layer is 10 layers at the maximum.
  • SiH 4 gas containing no chlorine atom is used as a raw material for silicon epitaxial growth when an epitaxial layer in contact with the atomic layer is formed. This is because chlorine atoms are included in the epitaxial growth gas, so that even if an oxygen atomic layer is formed, the gas is etched by chlorine.
  • the oxygen atomic layer needs to be 5 nm or less, and is preferably as thin as possible, and it is preferable to introduce an amount sufficient to adsorb a single atom. If the oxygen atomic layer is too thick, the silicon layer is oxidized, and the second silicon epitaxial layer cannot be deposited on the oxygen atomic layer. Precisely, even if silicon epitaxial growth is performed on such an oxygen atomic layer, it is not epitaxial growth but becomes amorphous silicon or is polycrystallized.
  • the oxygen atomic layer only needs to be able to deposit one Langmuir layer using the principle of isothermal adsorption.
  • One skilled in the art can deposit one Langmuir layer. Although it depends on the chamber size of the furnace, it can be solved by flowing an oxygen gas of about 10 L / min (for example, 5 L / min to 15 L / min). Further, for example, the pressure and time conditions can be about 1 ⁇ 10 ⁇ 8 Torr (1.33 ⁇ 10 ⁇ 6 Pa) and about 100 seconds. It can be 10 ⁇ 500 ⁇ 6 Torr or more and 1 ⁇ 10 ⁇ 9 Torr or less and 10 to 500 seconds.
  • the temperature can be in a range not exceeding the epitaxial growth temperature.
  • the growth rate is preferably 0.005 nm / second or less.
  • the manufacturing method of an epitaxial wafer is demonstrated more concretely.
  • SiH 4 gas not containing chlorine as a source gas
  • SiH 4 gas is introduced as a source gas from a position at least 5 nm away from the position where the oxygen atomic layer 31 is formed, and the silicon epitaxial layer 21 is grown with a gas not containing chlorine.
  • oxygen gas is introduced to grow an oxygen atomic layer 31 having a thickness of 5 nm or less.
  • SiH 4 gas is introduced as a raw material gas to a position at least 5 nm away from the position where the oxygen atomic layer 31 is formed, and the silicon epitaxial layer 22 is grown with a gas not containing chlorine.
  • FIG. 3 shows the supply image of each gas.
  • the oxygen atomic layer is preferably formed as a single atomic layer.
  • Oxygen can be grown in a single atom (delta dope) by setting conditions so that 1 Langmuir (isothermal monoatomic adsorption) amount is introduced so that oxygen is in an atomic layer adsorption.
  • the formation of the epitaxial layer in contact with the oxygen atomic layer 31 may be performed using SiH 4 gas.
  • a region other than a region formed using SiH 4 gas can be formed using SiH 2 Cl 2 gas or SiHCl 3 gas.
  • the oxygen atomic layer 31 is completely covered with SiH 4 , so that the epitaxial layer in the region separated by more than 5 nm from the oxygen atomic layer is formed.
  • SiH 4 containing no chlorine gas is formed, may be used SiH 2 Cl 2 or SiHCl 3.
  • the epitaxial layer When the epitaxial layer is formed thick in a region away from the oxygen atomic layer, the epitaxial layer can be formed in a shorter time by using SiH 2 Cl 2 or SiHCl 3 . Since the growth rate when SiH 4 gas is used is slow, for example, when an epitaxial layer having a thickness of 100 nm or more is formed, it is preferable to switch to SiH 2 Cl 2 or SiHCl 3 in the middle. Thereby, high productivity and low cost can be achieved.
  • the growth temperature of the silicon epitaxial layer is preferably in the range of 500 ° C. or higher and 800 ° C. or lower.
  • a silicon epitaxial wafer having an oxygen atomic layer manufactured by the method of the present invention can be expected to have a proximity gettering effect and an improvement in device yield.
  • the epitaxial wafer 100 having the above-described epitaxial layer 50 having an oxygen atomic layer is used except that a carbon atomic layer is employed as the atomic layer 31 instead of the oxygen atomic layer. The same.
  • a silicon epitaxial wafer having a carbon atom layer manufactured by the method of the present invention can be expected to have a proximity gettering effect and an improvement in device yield. Furthermore, since carbon has a smaller atomic radius than silicon, it has the effect of distorting the silicon layer grown on the carbon atomic layer, and can also be expected to improve the carrier mobility of the device.
  • the epitaxial wafer 100 having the above-described epitaxial layer 50 having the oxygen atomic layer, except that a nitrogen atomic layer is employed as the atomic layer 31 instead of the oxygen atomic layer, The same.
  • a gas not containing chlorine atoms but containing nitrogen atoms is introduced to grow a nitrogen atom layer 31 having a thickness of 5 nm or less.
  • NH 3 gas ammonia gas
  • epitaxial growth is performed using SiH 4 gas as a raw material.
  • the supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, during the growth of the silicon epitaxial layer, NH 3 gas is introduced for a short time, that is, delta doping is performed.
  • an epitaxial wafer having improved silicon substrate strength by promoting oxygen precipitation by nitrogen is obtained.
  • the nitrogen atom layer is 10 layers at the maximum.
  • the effect of stopping the slip of the silicon layer grown on the atomic layer can also be expected by the nitrogen atomic layer.
  • the epitaxial wafer 100 having the epitaxial layer 50 having the oxygen atomic layer described above is used except that a germanium atomic layer is employed as the atomic layer 31 instead of the oxygen atomic layer. The same.
  • epitaxial growth using SiH 4 gas as a raw material is performed.
  • the supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, during the growth of the silicon epitaxial layer, tetramethyl germanium gas is introduced for a short time, that is, delta doping is performed.
  • silicone mutually can be obtained.
  • silicon is more easily oxidized than Ge. Therefore, it becomes possible to form a stacked structure of Ge / SiO 2 / Ge / SiO 2 , which can be applied to optical devices. An expected substrate can be obtained.
  • the silicon epitaxial layer 21 is formed.
  • the SiH 4 gas was purged by introducing a gas containing tin atoms containing no chlorine atoms, to grow less tin atoms layer 31 thickness of 5 nm.
  • This gas is particularly preferably an organometallic gas containing tin (such as tetramethyltin). In the following description, a case where tetramethyltin gas is used will be described.
  • the supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, during the growth of the silicon epitaxial layer, tetramethyltin gas is introduced for a short time, that is, delta doping is performed.
  • Sn As a practical method of using Sn, it can be used as a surface modification when various elements such as Ge are grown on silicon. For this purpose, it is possible to grow Ge by the same method after growing Sn by this method.
  • the epitaxial wafer 100 of the aspect shown in FIG. 1 was manufactured as follows. First, a first epitaxial growth was performed using a silicon substrate 10 having a resistivity of 10 ⁇ ⁇ cm and boron doping and a diameter of 200 mm (silicon epitaxial layer 21). The silicon source gas was grown as SiH 4 at 550 ° C. Although the time for flowing the silicon source gas is set according to the film thickness, since the slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the silicon epitaxial layer 21 is set to 10 nm.
  • the temperature was raised to 600 ° C. to increase the growth rate to grow a 3 ⁇ m silicon epitaxial layer, and an epitaxial wafer 100 having an oxygen atomic layer 31 in the epitaxial layer 50 was manufactured.
  • the epitaxial wafer 200 of the aspect shown in FIG. 2 was manufactured as follows. First, a first epitaxial growth was performed using a silicon substrate 10 having a resistivity of 10 ⁇ ⁇ cm and boron doping and a diameter of 200 mm (silicon epitaxial layer 21). The silicon source gas was grown as SiH 4 at 550 ° C. Although the time for flowing the silicon source gas is set in accordance with the film thickness, since a slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the first silicon epitaxial layer 21 is set to 10 nm.
  • oxygen gas 6 L / min was introduced into the reactor at 1 ⁇ 10 ⁇ 8 Torr for 100 seconds to grow the oxygen atomic layer 31 by one atomic layer.
  • a silicon source gas was introduced under the same conditions as those for the first silicon epitaxial layer 21 to form a second silicon epitaxial layer 22 having a thickness of 10 nm.
  • an oxygen atomic layer 32 was deposited on the second silicon epitaxial layer 22 under the same conditions as the oxygen atomic layer 31, and a third silicon epitaxial layer 23 was further deposited under the same conditions as the first silicon epitaxial layer 21.
  • oxygen atom layers (33, 34, 35) and silicon epitaxial layers (24, 25, 26) are alternately deposited under the same conditions, so that the oxygen atom layer / silicon epitaxial layer has a set 40 of five layers.
  • An epitaxial wafer 200 including the epitaxial layer 60 was manufactured.
  • SiH 2 Cl 2 was grown as a part of the 3 ⁇ m epitaxial layer 26 as a raw material.
  • a diffusion region of about 1 ⁇ m may be formed as an active region for manufacturing an actual device.
  • the silicon source gas was introduced under the same conditions as the first epitaxial layer to try to form the second epitaxial layer.
  • the oxygen atomic layer was thick, and epitaxial growth was not possible, resulting in polycrystalline silicon. It was. Thus, it can be seen that when the oxygen atomic layer is thick, the second silicon epitaxial layer does not become a single crystal.
  • the epitaxial wafer 100 having the aspect shown in FIG. 1 and having the carbon atom layer 31 as an atomic layer in the epitaxial layer was manufactured as follows. First, a first epitaxial growth was performed using a silicon substrate 10 having a resistivity of 10 ⁇ ⁇ cm and boron doping and a diameter of 200 mm (silicon epitaxial layer 21). The silicon source gas was grown as SiH 4 at 550 ° C. Although the time for flowing the silicon source gas is set according to the film thickness, since the slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the silicon epitaxial layer 21 is set to 10 nm.
  • the temperature was raised to 600 ° C. to increase the growth rate, and a 3 ⁇ m-thick silicon epitaxial layer was grown to manufacture an epitaxial wafer 100 having the carbon atom layer 31 in the epitaxial layer 50.
  • 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.

Abstract

The present invention is an epitaxial wafer production method in which an epitaxial layer is formed on a silicon substrate. The epitaxial wafer production method includes a step of forming, in the epitaxial layer, an atomic layer comprising atoms of at least one type of element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus and having a thickness of 5 nm or less. An epitaxial layer adjacent to the atomic layer is formed using SiH4 gas. Due to this configuration, provided is an epitaxial wafer production in which an atomic layer of oxygen or the like can be stably introduced into an epitaxial layer.

Description

エピタキシャルウェーハの製造方法Epitaxial wafer manufacturing method
　本発明は、エピタキシャルウェーハの製造方法に関する。 The present invention relates to a method for manufacturing an epitaxial wafer.
　固体撮像素子やその他のトランジスタをはじめとした半導体素子を形成するシリコン基板には、重金属をはじめとした素子特性を狂わせる元素をゲッタリングする機能を持つことが求められる。ゲッタリングにはシリコン基板裏面に多結晶シリコン（Ｐｏｌｙ－Ｓｉ）層を持たせたり、ブラスト加工によりダメージを持たせた層を形成する方法や、シリコン基板の高濃度ボロンを利用したり、析出物を形成させたりとさまざまな手法が提案、実用化されている。酸素析出によるゲッタリングは電気陰性度が大きい酸素に対して、イオン化傾向が大きい（電気陰性度が小さい）金属を取り込むことでゲッタリングする。 A silicon substrate on which a semiconductor element such as a solid-state imaging element or other transistor is formed is required to have a function of gettering elements that detract from element characteristics such as heavy metals. For gettering, there is a method of forming a polycrystalline silicon (Poly-Si) layer on the back of the silicon substrate, forming a layer damaged by blasting, utilizing the high-concentration boron of the silicon substrate, Various methods have been proposed and put into practical use. In gettering by oxygen precipitation, gettering is performed by incorporating a metal having a large ionization tendency (small electronegativity) with respect to oxygen having a large electronegativity.
　また素子の活性領域近傍にゲッタリング層を形成する、いわゆる近接ゲッタリングも提案されている。例えば、炭素をイオン注入した基板の上にシリコンをエピタキシャル成長させた基板などがある。ゲッタリングは、ゲッタリングサイト（金属が単元素で存在するよりもサイトで結合やクラスタリングすることで系全体のエネルギーが低下する）まで元素が拡散する必要がある。シリコン中に含まれる金属元素の拡散係数は元素により異なり、また近年のプロセス低温化によりゲッタリングサイトまで金属が拡散することが出来なくなることを考慮して近接ゲッタリングの手法が提案されている。 Also, so-called proximity gettering in which a gettering layer is formed in the vicinity of the active region of the element has been proposed. For example, there is a substrate obtained by epitaxially growing silicon on a substrate into which carbon is ion-implanted. In the gettering, the element needs to diffuse to the gettering site (the energy of the entire system is reduced by bonding or clustering at the site rather than the metal being present as a single element). Proximity gettering methods have been proposed in consideration of the fact that the diffusion coefficient of metal elements contained in silicon varies from element to element, and that metals cannot diffuse to the gettering site due to recent process low temperatures.
　近接ゲッタリングに酸素を用いることが出来れば、非常に有力なゲッタリング層をもったシリコン基板となると考えられる。特に、エピタキシャル層の途中に酸素原子層を有するエピタキシャルウェーハであれば、近年の低温プロセスにおいても確実に金属不純物をゲッタリングすることができる。 If oxygen can be used for proximity gettering, a silicon substrate having a very powerful gettering layer is considered. In particular, an epitaxial wafer having an oxygen atomic layer in the middle of an epitaxial layer can reliably getter metal impurities even in recent low-temperature processes.
　以上、金属不純物をゲッタリングすることを中心に述べてきたが、例えば、酸素の効果としては、ＣＶＤ酸化膜を裏面に形成することでエピタキシャル成長時のオートドープを防ぐ効果が知られている。 As described above, the gettering of metal impurities has been mainly described. For example, as an effect of oxygen, an effect of preventing autodoping during epitaxial growth is known by forming a CVD oxide film on the back surface.
　さらに酸素以外では、シリコンと同じＩＶ族（１４族）の炭素においては、炭素によるゲッタリング効果、Ｇｅではシリコン酸化膜との組み合わせによる光デバイスへの応用、ＳｎはＧｅ等をシリコン上に成長する際の、表面改質の効果、ＩＶ族以外では、窒素では析出促進による強度の向上など、シリコンと他元素の組み合わせによるいろいろな効果が期待され応用されている。 In addition to oxygen, in the same group IV (group 14) carbon as silicon, gettering effect due to carbon, application to optical devices in combination with silicon oxide film in Ge, Sn grows Ge etc. on silicon At the same time, other than group IV, other than group IV, various effects of combinations of silicon and other elements such as improvement of strength by promoting precipitation are expected and applied in nitrogen.
　先行技術について言及する。特許文献１は、構造としてはシリコンの上に酸素の薄い層を形成しさらにシリコンを成長させる方法である。この方法は、ＡＬＤ（「Ａｔｏｍｉｃ　ｌａｙｅｒ　ｄｅｐｏｓｉｔｉｏｎ」、「原子層堆積法」）をベースとした技術である。ＡＬＤは対象原子を含む分子を吸着させ、その後分子中の不要な原子（分子）を乖離・脱離させる方法であり、表面結合を利用し非常に精度よくまた、反応制御性が良好であり幅広く用いられているが、不要分子を脱離させることで、原子層形成に不要かつ意図しない挙動を示す不純物を生成するという弱点がある。実際に、ＡＬＤ法では、酸素層を形成するために炭素を含む分子を利用するので、炭素（不要な炭素）の影響が懸念される。 Refer to the prior art. Patent Document 1 is a method of forming a thin layer of oxygen on silicon and further growing silicon. This method is based on ALD (“Atomic layer deposition”, “Atomic layer deposition method”). ALD is a method to adsorb molecules containing target atoms and then dissociate and desorb unnecessary atoms (molecules) in the molecule. It uses surface bonding, has high accuracy, has good reaction controllability, and is widely used. Although it is used, there is a weak point that impurities that are unnecessary and unintentional for forming an atomic layer are generated by eliminating unnecessary molecules. Actually, since the ALD method uses molecules containing carbon to form an oxygen layer, there is a concern about the influence of carbon (unnecessary carbon).
　特許文献２は、特許文献１と同様の基板を実現するためのリアクタに関する技術であるが、こちらは原料ガス・手法としてＭＯＶＰＥ（有機金属気相成長法）を想定している。ＭＯＶＰＥであるために有機金属を利用する。反応制御は容易であるが、酸素原子層を形成する際に不要な不純物金属の懸念がある。特にシリコン基板そのものへの適用には金属汚染が懸念される。 Patent Document 2 is a technology related to a reactor for realizing a substrate similar to that of Patent Document 1, but this assumes MOVPE (metal organic chemical vapor deposition) as a source gas / method. An organic metal is used to be MOVPE. Although reaction control is easy, there is a concern of unnecessary impurity metals when forming the oxygen atomic layer. In particular, there is a concern about metal contamination when applied to the silicon substrate itself.
　以上のように、これら特許文献１、２の技術はＡＬＤないしは、ＭＯＶＰＥというそれぞれの技術に基づいて行われている。 As described above, the techniques of Patent Documents 1 and 2 are performed based on respective techniques of ALD or MOVPE.
　特許文献３、４は、シリコン基板に酸素原子層を複数導入することで、デバイス特性の改善（移動度）向上が可能になることを示しているが、具体的な成長方法には言及していない。 Patent Documents 3 and 4 show that by introducing a plurality of oxygen atom layers into a silicon substrate, device characteristics (mobility) can be improved, but no specific growth method is mentioned. Absent.
　酸素以外の原子層をシリコン基板に導入する先行技術としては、たとえば特許文献５に記載のように、シリコンの表面に急峻なビスマスのプロファイルを作りこむ方法が開示されている。特許文献５ではデルタドープと記載されており、線状にドーパントを埋め込む基礎技術として開示されているが、ウェーハ全面に展開することは困難であると考えられる。 As a prior art for introducing an atomic layer other than oxygen into a silicon substrate, a method of creating a steep bismuth profile on the surface of silicon as disclosed in, for example, Patent Document 5 is disclosed. Patent Document 5 describes delta doping, which is disclosed as a basic technique for embedding a dopant in a linear shape, but it is considered difficult to spread the entire surface of the wafer.
特開２０１４－１６５４９４号公報JP 2014-165494 A 特開２０１３－１９７２９１号公報JP 2013-197291 A 米国特許第７，１５３，７６３号明細書US Pat. No. 7,153,763 米国特許第７，２６５，００２号明細書US Pat. No. 7,265,002 特開２０００－００３８７７号公報JP 2000-003877 A
　上述の問題点に鑑み、本発明は、酸素等の原子層をエピタキシャル層に安定的に導入することができるエピタキシャルウェーハの製造方法を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide an epitaxial wafer manufacturing method capable of stably introducing an atomic layer such as oxygen into an epitaxial layer.
　上記目的を達成するために、本発明は、シリコン基板上にエピタキシャル層を形成するエピタキシャルウェーハの製造方法であって、前記エピタキシャル層中に、酸素、炭素、窒素、ゲルマニウム、スズ、ホウ素及びリンからなる群から選ばれる１種の元素の原子からなり、厚さが５ｎｍ以下である原子層を形成する工程を有し、前記原子層に接するエピタキシャル層の形成を、ＳｉＨ４ガスを用いて行うことを特徴とするエピタキシャルウェーハの製造方法を提供する。 In order to achieve the above object, the present invention provides an epitaxial wafer manufacturing method for forming an epitaxial layer on a silicon substrate, wherein oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus are contained in the epitaxial layer. A step of forming an atomic layer made of atoms of one element selected from the group and having a thickness of 5 nm or less, and forming an epitaxial layer in contact with the atomic layer using SiH 4 gas An epitaxial wafer manufacturing method is provided.
　このようなエピタキシャルウェーハの製造方法であれば、エピタキシャル層中に、酸素等の元素の原子からなる原子層を安定的に形成することができる。特に、酸素等の元素の原子からなる原子層に接するエピタキシャル層の形成を、分子中に塩素原子を有しないＳｉＨ４ガスを用いて行うため、酸素等の原子層のエッチングを防止できる。 With such an epitaxial wafer manufacturing method, an atomic layer made of atoms of elements such as oxygen can be stably formed in the epitaxial layer. In particular, since the formation of an epitaxial layer in contact with an atomic layer made of atoms of elements such as oxygen is performed using SiH 4 gas having no chlorine atom in the molecule, etching of the atomic layer such as oxygen can be prevented.
　本発明のエピタキシャルウェーハの製造方法では、この場合、前記原子層を、１原子層として形成することができる。 In the epitaxial wafer manufacturing method of the present invention, in this case, the atomic layer can be formed as a single atomic layer.
　本発明では、このように、酸素等の原子層を１原子層として形成することもできる。また、そのような１原子層を形成する場合でも、本発明の方法であれば、安定して１原子層を形成することができる。 In the present invention, an atomic layer of oxygen or the like can be formed as a single atomic layer as described above. Even when such a single atomic layer is formed, the single atomic layer can be stably formed by the method of the present invention.
　また、前記エピタキシャル層の領域のうち、前記原子層に接し、少なくとも該原子層から５ｎｍまでの領域を、ＳｉＨ４ガスを用いて形成することが好ましい。 In addition, it is preferable that, of the region of the epitaxial layer, a region in contact with the atomic layer and at least 5 nm from the atomic layer is formed using SiH 4 gas.
　このように、エピタキシャル層の領域のうち、酸素等の原子層から５ｎｍまでの領域を、塩素を含まないＳｉＨ４ガスを用いて形成することにより、酸素等の原子層をより安定して形成することができる。 Thus, by forming the region from the atomic layer such as oxygen to 5 nm in the region of the epitaxial layer using SiH 4 gas not containing chlorine, the atomic layer such as oxygen is formed more stably. be able to.
　また、前記原子層を、前記エピタキシャル層中に複数層形成することができる。 Also, a plurality of the atomic layers can be formed in the epitaxial layer.
　本発明では、酸素等の原子層をエピタキシャル層中に複数層形成することもできる。また、このような構成を安定して形成することができる。 In the present invention, a plurality of atomic layers such as oxygen can be formed in the epitaxial layer. Moreover, such a structure can be formed stably.
　また、前記エピタキシャル層の領域のうち、前記ＳｉＨ４ガスを用いて形成する領域以外の領域を、ＳｉＨ２Ｃｌ２ガス又はＳｉＨＣｌ３ガスを用いて形成することが好ましい。 In addition, it is preferable that a region other than a region formed using the SiH 4 gas among the regions of the epitaxial layer is formed using a SiH 2 Cl 2 gas or a SiHCl 3 gas.
　このように、エピタキシャル層のうち、ＳｉＨ４ガスを用いて形成する領域以外をＳｉＨ２Ｃｌ２ガス又はＳｉＨＣｌ３ガスを用いて形成することにより、酸素等の原子層から離れた領域においてエピタキシャル層を厚く形成することができる。その結果、より短時間にエピタキシャル層全体を形成することができるので、生産性及びコストに資する。 Thus, among the epitaxial layer, by forming with SiH 2 Cl 2 gas or SiHCl 3 gas other than the region formed by using a SiH 4 gas, the epitaxial layer in areas away from the atoms of oxygen, such as layer It can be formed thick. As a result, the entire epitaxial layer can be formed in a shorter time, which contributes to productivity and cost.
　また、前記原子層の形成を、酸素原子層を形成する場合は酸素ガスを、炭素原子層を形成する場合はＣＨ４ガスを、窒素原子層を形成する場合はＮＨ３ガスを、ゲルマニウム原子層を形成する場合はＧｅを含む有機金属ガスを、スズ原子層を形成する場合はＳｎを含む有機金属ガスを、ホウ素原子層を形成する場合はＢ２Ｈ６ガスを、リン原子層を形成する場合はＰＨ３ガスを、用いて行うことができる。 The atomic layer is formed by oxygen gas when forming an oxygen atomic layer, CH 4 gas when forming a carbon atomic layer, NH 3 gas when forming a nitrogen atomic layer, and a germanium atomic layer. Is formed, an organometallic gas containing Ge is formed, an organometallic gas containing Sn is formed when a tin atomic layer is formed, B 2 H 6 gas is formed when a boron atomic layer is formed, and a phosphorus atomic layer is formed. In some cases, PH 3 gas can be used.
　これらのガスを使用することにより、酸素等の原子層を形成することができる。 An atomic layer such as oxygen can be formed by using these gases.
　本発明により、先端デバイスで採用されるシリコンエピタキシャルウェーハにおいて、酸素等の原子層をエピタキシャル層に安定的に導入することができる。また、酸素原子層による近接ゲッタリング効果を有する近接ゲッタリング基板や、ＩＶ族元素及び窒素、ドーパント等を用いた複合機能を有する機能性基板を製造することが可能となる。 According to the present invention, an atomic layer such as oxygen can be stably introduced into the epitaxial layer in the silicon epitaxial wafer employed in the advanced device. In addition, it is possible to manufacture a proximity gettering substrate having a proximity gettering effect by an oxygen atomic layer and a functional substrate having a composite function using a group IV element, nitrogen, a dopant, and the like.
本発明によって製造することができる、酸素等の原子層を有するエピタキシャルウェーハの一例を示す模式的な断面図である。It is typical sectional drawing which shows an example of the epitaxial wafer which has atomic layers, such as oxygen, which can be manufactured by this invention. 本発明によって製造することができる、酸素等の原子層を複数有するエピタキシャルウェーハの一例を示す模式的な断面図である。It is typical sectional drawing which shows an example of the epitaxial wafer which has a plurality of atomic layers, such as oxygen, which can be manufactured by this invention. 本発明のエピタキシャルウェーハを製造する成長レシピの概念図である。It is a conceptual diagram of the growth recipe which manufactures the epitaxial wafer of this invention.
　以下、本発明について、実施態様の一例として、図を参照しながら詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in detail as an example of an embodiment with reference to the drawings, but the present invention is not limited thereto.
　本発明は、シリコン基板上にエピタキシャル層を形成するエピタキシャルウェーハの製造方法であり、エピタキシャル層中に、酸素、炭素、窒素、ゲルマニウム、スズ、ホウ素及びリンからなる群から選ばれる１種の元素の原子からなり、厚さが５ｎｍ以下である原子層を形成する工程を有する。本発明においては、さらに、上記の原子層に接するエピタキシャル層の形成を、ＳｉＨ４ガスを用いて行う。以降の説明では、エピタキシャル層中に形成する、酸素、炭素、窒素、ゲルマニウム、スズ、ホウ素及びリンのうち１種類の元素の原子からなる原子層を単に「原子層」と称する。 The present invention is an epitaxial wafer manufacturing method for forming an epitaxial layer on a silicon substrate. In the epitaxial layer, one element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus is used. A step of forming an atomic layer made of atoms and having a thickness of 5 nm or less. In the present invention, the epitaxial layer in contact with the atomic layer is further formed using SiH 4 gas. In the following description, an atomic layer formed of atoms of one element among oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus formed in the epitaxial layer is simply referred to as “atomic layer”.
［エピタキシャル層中に酸素原子層を導入する場合］
　まず、シリコン基板上のエピタキシャル層中に酸素原子層を導入する場合について説明する。 [When introducing an oxygen atom layer into the epitaxial layer]
First, a case where an oxygen atomic layer is introduced into an epitaxial layer on a silicon substrate will be described.
　図１に本発明のエピタキシャルウェーハの製造方法によって製造することができる、酸素原子層を有するエピタキシャルウェーハ１００の模式的な断面図を示す。エピタキシャルウェーハ１００は、シリコン基板１０の上にエピタキシャル層５０が形成されており、エピタキシャル層５０中に、酸素原子からなり、厚さが５ｎｍ以下である原子層（酸素原子層）３１が形成される。シリコン基板１０と酸素原子層３１の間には、シリコンからなるシリコンエピタキシャル層２１が形成される。シリコンエピタキシャル層２１の上に酸素原子層３１が形成され、酸素原子層３１の上にシリコンエピタキシャル層２２が形成される。図１の例では、シリコンエピタキシャル層２１、酸素原子層３１、シリコンエピタキシャル層２２からなるエピタキシャル層５０が形成される。 FIG. 1 shows a schematic cross-sectional view of an epitaxial wafer 100 having an oxygen atomic layer, which can be manufactured by the epitaxial wafer manufacturing method of the present invention. In the epitaxial wafer 100, an epitaxial layer 50 is formed on a silicon substrate 10, and an atomic layer (oxygen atomic layer) 31 made of oxygen atoms and having a thickness of 5 nm or less is formed in the epitaxial layer 50. . A silicon epitaxial layer 21 made of silicon is formed between the silicon substrate 10 and the oxygen atomic layer 31. An oxygen atomic layer 31 is formed on the silicon epitaxial layer 21, and a silicon epitaxial layer 22 is formed on the oxygen atomic layer 31. In the example of FIG. 1, an epitaxial layer 50 including a silicon epitaxial layer 21, an oxygen atom layer 31, and a silicon epitaxial layer 22 is formed.
　上記のように、酸素原子層３１を形成する場合の製造方法としては、以下の通りである。シリコン基板１０上にエピタキシャル成長を行って、まず、シリコンエピタキシャル層２１を形成する。そのシリコンエピタキシャル層２１の上に酸素原子層３１を成長させる。さらに酸素原子層３１の上にシリコンをエピタキシャル成長してシリコンエピタキシャル層２２を形成する。これにより、酸素原子層３１を有するエピタキシャル層５０全体を形成し、エピタキシャルウェーハ１００を形成する。 As described above, the manufacturing method for forming the oxygen atomic layer 31 is as follows. Epitaxial growth is performed on the silicon substrate 10 to first form a silicon epitaxial layer 21. An oxygen atomic layer 31 is grown on the silicon epitaxial layer 21. Further, silicon is epitaxially grown on the oxygen atom layer 31 to form the silicon epitaxial layer 22. Thereby, the entire epitaxial layer 50 having the oxygen atomic layer 31 is formed, and the epitaxial wafer 100 is formed.
　図１では酸素原子層は１層であるが、酸素原子層、シリコンエピタキシャル成長を繰り返し、酸素原子層を複数形成することも可能である。エピタキシャル層中に酸素原子層を複数形成したエピタキシャルウェーハを図２に示した。すなわち、図２に示したエピタキシャルウェーハ２００を製造する場合には、以下のようにして製造することができる。まず、シリコン基板１０の上にシリコンエピタキシャル層２１を形成する。シリコンエピタキシャル層２１の上に、酸素原子層３１を形成する。さらに、酸素原子層３１の上に、シリコンエピタキシャル層２２を形成する。ここまでは図１の態様と同様であるが、図２の態様では、さらに、酸素原子層３２、シリコンエピタキシャル層２３、酸素原子層３３、シリコンエピタキシャル層２４、酸素原子層３４、シリコンエピタキシャル層２５、酸素原子層３５、シリコンエピタキシャル層２６と形成していく。これにより、シリコンエピタキシャル層と酸素原子層の組が５組繰り返された構造４０が形成された、エピタキシャル層６０を形成することができる。このように、酸素原子層を複数形成することにより、より優れたゲッタリング効果を有するエピタキシャルウェーハが得られる。このとき、酸素原子層は最大でも１０層あれば十分である。 In FIG. 1, there is one oxygen atom layer, but it is also possible to repeat the oxygen atom layer and silicon epitaxial growth to form a plurality of oxygen atom layers. An epitaxial wafer having a plurality of oxygen atom layers formed in the epitaxial layer is shown in FIG. That is, when the epitaxial wafer 200 shown in FIG. 2 is manufactured, it can be manufactured as follows. First, the silicon epitaxial layer 21 is formed on the silicon substrate 10. An oxygen atom layer 31 is formed on the silicon epitaxial layer 21. Further, the silicon epitaxial layer 22 is formed on the oxygen atom layer 31. The process up to this point is the same as that of FIG. 1, but in the aspect of FIG. 2, the oxygen atom layer 32, silicon epitaxial layer 23, oxygen atom layer 33, silicon epitaxial layer 24, oxygen atom layer 34, silicon epitaxial layer 25 are further provided. Then, an oxygen atom layer 35 and a silicon epitaxial layer 26 are formed. Thereby, the epitaxial layer 60 in which the structure 40 in which five sets of the silicon epitaxial layer and the oxygen atom layer are repeated is formed can be formed. Thus, by forming a plurality of oxygen atom layers, an epitaxial wafer having a better gettering effect can be obtained. At this time, it is sufficient that the oxygen atom layer is 10 layers at the maximum.
　本発明では、原子層に接するエピタキシャル層を形成するときのシリコンエピタキシャル成長の原料に、塩素原子を含まないＳｉＨ４ガスを利用する。エピタキシャル成長用ガスに塩素原子が含まれることで、酸素原子層を形成しても塩素によりエッチングされてしまうからである。 In the present invention, SiH 4 gas containing no chlorine atom is used as a raw material for silicon epitaxial growth when an epitaxial layer in contact with the atomic layer is formed. This is because chlorine atoms are included in the epitaxial growth gas, so that even if an oxygen atomic layer is formed, the gas is etched by chlorine.
　また酸素原子層は、５ｎｍ以下とすることが必要であり、また、できるだけ薄い方が好ましく、単原子吸着する程度の量を導入することが好ましい。酸素原子層が５ｎｍより厚すぎるとシリコン層が酸化されてしまい、酸素原子層の上に第２のシリコンエピタキシャル層を堆積することが出来なくなる。正確には、そのような酸素原子層上にシリコンエピタキシャル成長を行おうとしても、エピタキシャル成長でなくアモルファスシリコンとなってしまったり、多結晶化（ポリ化）してしまう。 Also, the oxygen atomic layer needs to be 5 nm or less, and is preferably as thin as possible, and it is preferable to introduce an amount sufficient to adsorb a single atom. If the oxygen atomic layer is too thick, the silicon layer is oxidized, and the second silicon epitaxial layer cannot be deposited on the oxygen atomic layer. Precisely, even if silicon epitaxial growth is performed on such an oxygen atomic layer, it is not epitaxial growth but becomes amorphous silicon or is polycrystallized.
　酸素原子層は、等温吸着の原理を用いて、１ラングミュアー層の堆積が出来ればよい。当業者であれば、１ラングミュアー層の堆積を行うことが可能である。炉のチャンバーサイズにもよるが、１０Ｌ／分程度（例えば、５Ｌ／分以上１５Ｌ／分以下）の酸素ガスを流すことで解決できる。また、例えば、圧力及び時間の条件は、１×１０－８Ｔｏｒｒ（１．３３×１０－６Ｐａ）程度、１００秒程度とすることができるが、必ずしもこのような条件でなくともよく、１×１０－６Ｔｏｒｒ以上１×１０－９Ｔｏｒｒ以下、１０～５００秒とすることができる。温度はエピタキシャル成長温度を超えない範囲とすることができる。成長レートは０．００５ｎｍ／秒以下とすることが好ましい。 The oxygen atomic layer only needs to be able to deposit one Langmuir layer using the principle of isothermal adsorption. One skilled in the art can deposit one Langmuir layer. Although it depends on the chamber size of the furnace, it can be solved by flowing an oxygen gas of about 10 L / min (for example, 5 L / min to 15 L / min). Further, for example, the pressure and time conditions can be about 1 × 10 −8 Torr (1.33 × 10 −6 Pa) and about 100 seconds. It can be 10 × 500 −6 Torr or more and 1 × 10 −9 Torr or less and 10 to 500 seconds. The temperature can be in a range not exceeding the epitaxial growth temperature. The growth rate is preferably 0.005 nm / second or less.
　図１の態様に基づいて、より具体的にエピタキシャルウェーハの製造方法を説明する。シリコン基板１０に酸素原子層３１を導入するために、シリコン基板１０上にエピタキシャル成長する際に、まず、原料ガスとして塩素を含まないＳｉＨ４ガスを用いたエピタキシャル成長を行い、シリコンエピタキシャル層２１を形成する。好ましくは、酸素原子層３１を形成する位置から少なくとも５ｎｍ離れた位置からは原料ガスとしてＳｉＨ４ガスを導入して塩素を含まないガスでシリコンエピタキシャル層２１を成長させる。ＳｉＨ４ガスをパージした後に酸素ガスを導入し、厚さ５ｎｍ以下の酸素原子層３１を成長させる。次に、酸素ガスをパージした後にＳｉＨ４ガスを原料として所望の厚さまでエピタキシャル成長を行う。好ましくは、酸素原子層３１を形成した位置から少なくとも５ｎｍ離れた位置まで原料ガスとしてＳｉＨ４ガスを導入して塩素を含まないガスでシリコンエピタキシャル層２２を成長させる。図３に各ガスの供給イメージを示す。 Based on the aspect of FIG. 1, the manufacturing method of an epitaxial wafer is demonstrated more concretely. In order to introduce the oxygen atomic layer 31 into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, first, epitaxial growth using SiH 4 gas not containing chlorine as a source gas is performed to form a silicon epitaxial layer 21. . Preferably, SiH 4 gas is introduced as a source gas from a position at least 5 nm away from the position where the oxygen atomic layer 31 is formed, and the silicon epitaxial layer 21 is grown with a gas not containing chlorine. After purging the SiH 4 gas, oxygen gas is introduced to grow an oxygen atomic layer 31 having a thickness of 5 nm or less. Next, after purging oxygen gas, epitaxial growth is performed to a desired thickness using SiH 4 gas as a raw material. Preferably, SiH 4 gas is introduced as a raw material gas to a position at least 5 nm away from the position where the oxygen atomic layer 31 is formed, and the silicon epitaxial layer 22 is grown with a gas not containing chlorine. FIG. 3 shows the supply image of each gas.
　上記のように、酸素原子層は、１原子層として形成することが好ましい。酸素の導入は酸素が１原子層吸着になるように１Ｌａｎｇｍｕｉｒ（等温単原子吸着）量を導入するように条件を設定することで、酸素を単原子成長可能となる（デルタドープ）。 As described above, the oxygen atomic layer is preferably formed as a single atomic layer. Oxygen can be grown in a single atom (delta dope) by setting conditions so that 1 Langmuir (isothermal monoatomic adsorption) amount is introduced so that oxygen is in an atomic layer adsorption.
　酸素原子層に接するエピタキシャル層を形成する際に、塩素（塩素原子）を含むガス（例えば、ＳｉＨ２Ｃｌ２ガス又はＳｉＨＣｌ３ガス等のクロロシラン類）を使用すると、塩素によるエッチング効果にてシリコン中に堆積した酸素層が無くなってしまう。そのため、酸素原子層３１に接するエピタキシャル層の形成を、ＳｉＨ４ガスを用いて行うことが必要である。特に、エピタキシャル層５０の領域のうち、酸素原子層３１に接し、少なくとも酸素原子層３１から５ｎｍまでの領域（シリコンエピタキシャル層２１、２２のうち、酸素原子層３１から５ｎｍまでの領域）を、ＳｉＨ４ガスを用いて形成することが好ましい。酸素原子層３１に塩素を含むガスが直接触れないことで、酸素原子層３１が塩素ガスによりエッチングされることを防ぐことが出来る。 When an epitaxial layer in contact with the oxygen atomic layer is formed, if a gas containing chlorine (chlorine atoms) (for example, chlorosilanes such as SiH 2 Cl 2 gas or SiHCl 3 gas) is used, the etching effect by chlorine causes silicon to The oxygen layer deposited on the surface disappears. Therefore, it is necessary to form an epitaxial layer in contact with the oxygen atomic layer 31 using SiH 4 gas. In particular, in the region of the epitaxial layer 50, the region in contact with the oxygen atomic layer 31 and at least from the oxygen atomic layer 31 to 5 nm (the region from the oxygen atomic layer 31 to 5 nm in the silicon epitaxial layers 21 and 22) is SiH. It is preferable to form using 4 gases. Since the gas containing chlorine is not in direct contact with the oxygen atom layer 31, the oxygen atom layer 31 can be prevented from being etched by the chlorine gas.
　すなわち、図１の酸素原子層３１のエッチングを防止するためには、酸素原子層３１に接するエピタキシャル層の形成を、ＳｉＨ４ガスを用いて行えばよく、反対に、エピタキシャル層の領域のうち、ＳｉＨ４ガスを用いて形成する領域以外の領域を、ＳｉＨ２Ｃｌ２ガス又はＳｉＨＣｌ３ガスを用いて形成することができる。特に、少なくとも酸素原子層３１から５ｎｍまでＳｉＨ４ガスを用いて形成すれば、酸素原子層３１がＳｉＨ４で完全にカバーされるので、酸素原子層から５ｎｍを超えて離れた領域のエピタキシャル層の形成では塩素ガスが含まれないＳｉＨ４に限定されず、ＳｉＨ２Ｃｌ２やＳｉＨＣｌ３を用いてもよい。酸素原子層から離れた領域においてエピタキシャル層を厚く形成する場合には、ＳｉＨ２Ｃｌ２やＳｉＨＣｌ３を用いることで、より短時間にエピタキシャル層を形成することができる。ＳｉＨ４ガスを用いた場合の成長速度は遅いので、例えば厚さが１００ｎｍ以上のエピタキシャル層を形成する場合は途中でＳｉＨ２Ｃｌ２やＳｉＨＣｌ３に切り替えることが好ましい。これにより、高生産性、低コストとすることができる。シリコンエピタキシャル層の成長温度は５００℃以上８００℃以下の範囲が好ましい。 That is, in order to prevent the etching of the oxygen atomic layer 31 in FIG. 1, the formation of the epitaxial layer in contact with the oxygen atomic layer 31 may be performed using SiH 4 gas. A region other than a region formed using SiH 4 gas can be formed using SiH 2 Cl 2 gas or SiHCl 3 gas. In particular, if at least the oxygen atomic layer 31 is formed from SiH 4 gas to 5 nm using the SiH 4 gas, the oxygen atomic layer 31 is completely covered with SiH 4 , so that the epitaxial layer in the region separated by more than 5 nm from the oxygen atomic layer is formed. is not limited to SiH 4 containing no chlorine gas is formed, may be used SiH 2 Cl 2 or SiHCl 3. When the epitaxial layer is formed thick in a region away from the oxygen atomic layer, the epitaxial layer can be formed in a shorter time by using SiH 2 Cl 2 or SiHCl 3 . Since the growth rate when SiH 4 gas is used is slow, for example, when an epitaxial layer having a thickness of 100 nm or more is formed, it is preferable to switch to SiH 2 Cl 2 or SiHCl 3 in the middle. Thereby, high productivity and low cost can be achieved. The growth temperature of the silicon epitaxial layer is preferably in the range of 500 ° C. or higher and 800 ° C. or lower.
　これは、図２の態様でも同様であり、酸素原子層３１、３２、３３、３４、３５の全てで、酸素原子層３１に接するエピタキシャル層の形成を、ＳｉＨ４ガスを用いて行うことが必要であり、また、これら酸素原子層から５ｎｍまでの領域を、ＳｉＨ４ガスを用いたエピタキシャル成長とすることが好ましい。 This is the same in the embodiment of FIG. 2, and it is necessary to form an epitaxial layer in contact with the oxygen atomic layer 31 by using SiH 4 gas in all of the oxygen atomic layers 31, 32, 33, 34, and 35. In addition, it is preferable that the region from the oxygen atomic layer to 5 nm is epitaxially grown using SiH 4 gas.
　本発明の方法で製造された、酸素原子層を有するシリコンエピタキシャルウェーハであれば、近接ゲッタリング効果を期待でき、素子歩留まりの向上も期待できる。 A silicon epitaxial wafer having an oxygen atomic layer manufactured by the method of the present invention can be expected to have a proximity gettering effect and an improvement in device yield.
［エピタキシャル層中に炭素原子層を導入する場合］
　次に、シリコン基板上のエピタキシャル層中に炭素原子層を導入する場合について説明する。基本的には、上記の酸素原子層を導入する場合と同様であるため、重複する記載は省略する。 [When carbon atom layer is introduced into the epitaxial layer]
Next, a case where a carbon atom layer is introduced into an epitaxial layer on a silicon substrate will be described. Since this is basically the same as the case where the oxygen atom layer is introduced, redundant description is omitted.
　エピタキシャルウェーハ１００に炭素原子層を導入する場合も、原子層３１として酸素原子層の代わりに炭素原子層が採用されること以外は、上記した酸素原子層を有するエピタキシャル層５０を有するエピタキシャルウェーハ１００と同じである。 Even when a carbon atomic layer is introduced into the epitaxial wafer 100, the epitaxial wafer 100 having the above-described epitaxial layer 50 having an oxygen atomic layer is used except that a carbon atomic layer is employed as the atomic layer 31 instead of the oxygen atomic layer. The same.
　この方法は、シリコン基板１０に炭素原子層３１を導入するために、シリコン基板１０へエピタキシャル成長する際に、まず、原料ガスとして塩素を含まないＳｉＨ４ガスを用いたエピタキシャル成長を行い、シリコンエピタキシャル層２１を形成する。ＳｉＨ４ガスをパージした後に、塩素原子を含まず炭素原子を含むガスを導入し、厚さ５ｎｍ以下の炭素原子層３１を成長させる。このガスとしては特にＣＨ４ガス（メタンガス）が好ましい。以下の説明ではＣＨ４ガスを用いる場合を説明する。次に、ＣＨ４ガスをパージした後にＳｉＨ４ガスを原料としたエピタキシャル成長を行う。各ガスの供給量（成長レシピ）は、酸素ガスの場合と同様である。すなわち、シリコンエピタキシャル層の成長の合間に、短時間ＣＨ４ガスを導入する、すなわちデルタドープを行うことになる。 In this method, in order to introduce the carbon atom layer 31 into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, first, epitaxial growth using SiH 4 gas containing no chlorine as a source gas is performed, and the silicon epitaxial layer 21 is formed. Form. After purging the SiH 4 gas, a gas not containing chlorine atoms but containing carbon atoms is introduced to grow a carbon atom layer 31 having a thickness of 5 nm or less. This gas is particularly preferably CH 4 gas (methane gas). In the following description, a case where CH 4 gas is used will be described. Next, after purging CH 4 gas, epitaxial growth is performed using SiH 4 gas as a raw material. The supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, between the growth of the silicon epitaxial layer, CH 4 gas is introduced for a short time, that is, delta doping is performed.
　本発明の方法で製造された炭素原子層を有するシリコンエピタキシャルウェーハであれば、近接ゲッタリング効果を期待でき、素子歩留まりの向上も期待できる。さらに、炭素はシリコンと比較して原子半径が小さいために、炭素原子層の上に成長されたシリコン層を歪ませる効果があり、デバイスのキャリア移動度向上も期待できる。 A silicon epitaxial wafer having a carbon atom layer manufactured by the method of the present invention can be expected to have a proximity gettering effect and an improvement in device yield. Furthermore, since carbon has a smaller atomic radius than silicon, it has the effect of distorting the silicon layer grown on the carbon atomic layer, and can also be expected to improve the carrier mobility of the device.
［エピタキシャル層中に窒素原子層を導入する場合］
　次に、シリコン基板上のエピタキシャル層中に窒素原子層を導入する場合について説明する。基本的には、上記の酸素原子層を導入する場合と同様であるため、重複する記載は省略する。 [When introducing a nitrogen atom layer into the epitaxial layer]
Next, the case where a nitrogen atom layer is introduced into the epitaxial layer on the silicon substrate will be described. Since this is basically the same as the case where the oxygen atom layer is introduced, redundant description is omitted.
　エピタキシャルウェーハ１００に窒素原子層を導入する場合も、原子層３１として酸素原子層の代わりに窒素原子層が採用されること以外は、上記した酸素原子層を有するエピタキシャル層５０を有するエピタキシャルウェーハ１００と同じである。 In the case where a nitrogen atomic layer is introduced into the epitaxial wafer 100, the epitaxial wafer 100 having the above-described epitaxial layer 50 having the oxygen atomic layer, except that a nitrogen atomic layer is employed as the atomic layer 31 instead of the oxygen atomic layer, The same.
　この方法は、シリコン基板１０に窒素原子層３１を導入するために、シリコン基板１０へエピタキシャル成長する際に、まず、原料ガスとして塩素を含まないＳｉＨ４ガスを用いたエピタキシャル成長を行い、シリコンエピタキシャル層２１を形成する。ＳｉＨ４ガスをパージした後に、塩素原子を含まず窒素原子を含むガスを導入し、厚さ５ｎｍ以下の窒素原子層３１を成長させる。このガスとしては特にＮＨ３ガス（アンモニアガス）が好ましい。以下の説明ではＮＨ３ガスを用いる場合を説明する。次に、ＮＨ３ガスをパージした後にＳｉＨ４ガスを原料としたエピタキシャル成長を行う。各ガスの供給量（成長レシピ）は、酸素ガスの場合と同様である。すなわち、シリコンエピタキシャル層の成長の合間に、短時間ＮＨ３ガスを導入する、すなわちデルタドープを行うことになる。 In this method, in order to introduce the nitrogen atomic layer 31 into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, first, epitaxial growth using SiH 4 gas containing no chlorine as a raw material gas is performed to obtain a silicon epitaxial layer 21. Form. After purging the SiH 4 gas, a gas not containing chlorine atoms but containing nitrogen atoms is introduced to grow a nitrogen atom layer 31 having a thickness of 5 nm or less. As this gas, NH 3 gas (ammonia gas) is particularly preferable. In the following description, a case where NH 3 gas is used will be described. Next, after purging NH 3 gas, epitaxial growth is performed using SiH 4 gas as a raw material. The supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, during the growth of the silicon epitaxial layer, NH 3 gas is introduced for a short time, that is, delta doping is performed.
　これにより、窒素による酸素析出が促進されシリコン基板強度が向上したエピタキシャルウェーハが得られる。このとき、窒素原子層は最大でも１０層あれば十分である。窒素原子層により、前記原子層の上に成長されたシリコン層のスリップを止める効果も期待できる。 As a result, an epitaxial wafer having improved silicon substrate strength by promoting oxygen precipitation by nitrogen is obtained. At this time, it is sufficient that the nitrogen atom layer is 10 layers at the maximum. The effect of stopping the slip of the silicon layer grown on the atomic layer can also be expected by the nitrogen atomic layer.
［エピタキシャル層中にゲルマニウム原子層を導入する場合］
　次に、シリコン基板上のエピタキシャル層中にゲルマニウム原子層を導入する場合について説明する。基本的には、上記の酸素原子層を導入する場合と同様であるため、重複する記載は省略する。 [When a germanium atomic layer is introduced into the epitaxial layer]
Next, the case where a germanium atomic layer is introduced into the epitaxial layer on the silicon substrate will be described. Since this is basically the same as the case where the oxygen atom layer is introduced, redundant description is omitted.
　エピタキシャルウェーハ１００にゲルマニウム原子層を導入する場合も、原子層３１として酸素原子層の代わりにゲルマニウム原子層が採用されること以外は、上記した酸素原子層を有するエピタキシャル層５０を有するエピタキシャルウェーハ１００と同じである。 Even when a germanium atomic layer is introduced into the epitaxial wafer 100, the epitaxial wafer 100 having the epitaxial layer 50 having the oxygen atomic layer described above is used except that a germanium atomic layer is employed as the atomic layer 31 instead of the oxygen atomic layer. The same.
　この方法は、シリコン基板１０にゲルマニウム原子層３１を導入するために、シリコン基板１０へエピタキシャル成長する際に、まず、原料ガスとして塩素を含まないＳｉＨ４ガスを用いたエピタキシャル成長を行い、シリコンエピタキシャル層２１を形成する。ＳｉＨ４ガスをパージした後に、塩素原子を含まずゲルマニウム原子を含むガスを導入し、厚さ５ｎｍ以下のゲルマニウム原子層３１を成長させる。このガスとしては特にゲルマニウムを含む有機金属ガス（テトラメチルゲルマニウム等）が好ましい。以下の説明ではテトラメチルゲルマニウムガスを用いる場合を説明する。次に、テトラメチルゲルマニウムガスをパージした後にＳｉＨ４ガスを原料としたエピタキシャル成長を行う。各ガスの供給量（成長レシピ）は、酸素ガスの場合と同様である。すなわち、シリコンエピタキシャル層の成長の合間に、短時間テトラメチルゲルマニウムガスを導入する、すなわちデルタドープを行うことになる。 In this method, in order to introduce the germanium atomic layer 31 into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, first, epitaxial growth using SiH 4 gas containing no chlorine as a source gas is performed, and the silicon epitaxial layer 21 is formed. Form. The SiH 4 gas was purged by introducing a gas containing germanium atoms containing no chlorine atoms, to grow less germanium atoms layer 31 thickness of 5 nm. As this gas, an organometallic gas containing germanium (tetramethyl germanium or the like) is particularly preferable. In the following description, the case of using tetramethyl germanium gas will be described. Next, after purging the tetramethyl germanium gas, epitaxial growth using SiH 4 gas as a raw material is performed. The supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, during the growth of the silicon epitaxial layer, tetramethyl germanium gas is introduced for a short time, that is, delta doping is performed.
　これにより、Ｇｅとシリコンを相互に積層した基板を得ることが出来る。こののち酸化雰囲気に基板をさらすことで、シリコンがＧｅに比べて酸化されやすいことから、Ｇｅ／ＳｉＯ２／Ｇｅ／ＳｉＯ２の積層構造を形成することが可能になり、光デバイスへの応用が期待される基板を得ることが可能になる。 Thereby, the board | substrate which laminated | stacked Ge and silicon | silicone mutually can be obtained. After that, by exposing the substrate to an oxidizing atmosphere, silicon is more easily oxidized than Ge. Therefore, it becomes possible to form a stacked structure of Ge / SiO 2 / Ge / SiO 2 , which can be applied to optical devices. An expected substrate can be obtained.
［エピタキシャル層中にスズ原子層を導入する場合］
　次に、シリコン基板上のエピタキシャル層中にスズ原子層を導入する場合について説明する。基本的には、上記の酸素原子層を導入する場合と同様であるため、重複する記載は省略する。 [When introducing a tin atomic layer into the epitaxial layer]
Next, a case where a tin atomic layer is introduced into an epitaxial layer on a silicon substrate will be described. Since this is basically the same as the case where the oxygen atom layer is introduced, redundant description is omitted.
　エピタキシャルウェーハ１００にスズ原子層を導入する場合も、原子層３１として酸素原子層の代わりにスズ原子層が採用されること以外は、上記した酸素原子層を有するエピタキシャル層５０を有するエピタキシャルウェーハ１００と同じである。 Even when a tin atomic layer is introduced into the epitaxial wafer 100, the epitaxial wafer 100 having the above-described epitaxial layer 50 having an oxygen atomic layer, except that a tin atomic layer is adopted as the atomic layer 31 instead of the oxygen atomic layer, The same.
　この方法は、シリコン基板１０にスズ原子層３１を導入するために、シリコン基板１０へエピタキシャル成長する際に、まず、原料ガスとして塩素を含まないＳｉＨ４ガスを用いたエピタキシャル成長を行い、シリコンエピタキシャル層２１を形成する。ＳｉＨ４ガスをパージした後に、塩素原子を含まずスズ原子を含むガスを導入し、厚さ５ｎｍ以下のスズ原子層３１を成長させる。このガスとしては特にスズを含む有機金属ガス（テトラメチルスズ等）が好ましい。以下の説明ではテトラメチルスズガスを用いる場合を説明する。次に、テトラメチルスズガスをパージした後にＳｉＨ４ガスを原料としたエピタキシャル成長を行う。各ガスの供給量（成長レシピ）は、酸素ガスの場合と同様である。すなわち、シリコンエピタキシャル層の成長の合間に、短時間テトラメチルスズガスを導入する、すなわちデルタドープを行うことになる。 In this method, in order to introduce the tin atomic layer 31 into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, first, epitaxial growth using SiH 4 gas containing no chlorine as a source gas is performed, and the silicon epitaxial layer 21 is formed. Form. The SiH 4 gas was purged by introducing a gas containing tin atoms containing no chlorine atoms, to grow less tin atoms layer 31 thickness of 5 nm. This gas is particularly preferably an organometallic gas containing tin (such as tetramethyltin). In the following description, a case where tetramethyltin gas is used will be described. Next, after purging the tetramethyltin gas, epitaxial growth using SiH 4 gas as a raw material is performed. The supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, during the growth of the silicon epitaxial layer, tetramethyltin gas is introduced for a short time, that is, delta doping is performed.
　Ｓｎの実際的な使用方法としては、Ｇｅをはじめとする各種元素をシリコン上に成長させる際の表面改質としての利用が考えられる。この目的の場合であれば、Ｓｎを本法によって成長させたのち同じ方法にてＧｅを成長させることが可能である。 As a practical method of using Sn, it can be used as a surface modification when various elements such as Ge are grown on silicon. For this purpose, it is possible to grow Ge by the same method after growing Sn by this method.
［エピタキシャル層中にホウ素原子層又はリン原子層を導入する場合］
　次に、シリコン基板上のエピタキシャル層中にホウ素原子層又はリン原子層を導入する場合について説明する。基本的には、上記の酸素原子層を導入する場合と同様であるため、重複する記載は省略する。 [When introducing a boron atom layer or a phosphorus atom layer into the epitaxial layer]
Next, the case where a boron atom layer or a phosphorus atom layer is introduced into an epitaxial layer on a silicon substrate will be described. Since this is basically the same as the case where the oxygen atom layer is introduced, redundant description is omitted.
　エピタキシャルウェーハ１００にホウ素原子層又はリン原子層を導入する場合も、原子層３１として酸素原子層の代わりにホウ素原子層又はリン原子層が採用されること以外は、上記した酸素原子層を有するエピタキシャル層５０を有するエピタキシャルウェーハ１００と同じである。 Even when a boron atomic layer or a phosphorus atomic layer is introduced into the epitaxial wafer 100, an epitaxial having the oxygen atomic layer described above is used except that a boron atomic layer or a phosphorus atomic layer is employed instead of the oxygen atomic layer as the atomic layer 31. Same as epitaxial wafer 100 with layer 50.
　この方法は、シリコン基板１０にホウ素原子層３１又はリン原子層３１を導入するために、シリコン基板１０へエピタキシャル成長する際に、まず、原料ガスとして塩素を含まないＳｉＨ４ガスを用いたエピタキシャル成長を行い、シリコンエピタキシャル層２１を形成する。ＳｉＨ４ガスをパージした後に、塩素原子を含まずホウ素原子又はリン原子を含むガスを導入し、厚さ５ｎｍ以下のホウ素原子層３１又はリン原子層３１を成長させる。このガスとしては特にホウ素の場合はジボラン（Ｂ２Ｈ６）、リンの場合はホスフィン（ＰＨ３）ガスが好ましい。以下の説明ではこれらのドーパントガスを用いる場合を説明する。次に、これらのドーパントガスをパージした後にＳｉＨ４ガスを原料としたエピタキシャル成長を行う。各ガスの供給量（成長レシピ）は、酸素ガスの場合と同様である。すなわち、シリコンエピタキシャル層の成長の合間に、短時間ドーパントガスを導入する、すなわちデルタドープを行うことになる。 In this method, in order to introduce the boron atomic layer 31 or the phosphorus atomic layer 31 into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, first, epitaxial growth using SiH 4 gas containing no chlorine as a source gas is performed. Then, the silicon epitaxial layer 21 is formed. SiH 4 After the purge gas, and introducing a gas containing boron atoms or phosphorus atoms containing no chlorine atoms, to grow less boron atoms layer 31 or a phosphorus atom layer 31 thickness of 5 nm. This gas is preferably diborane (B 2 H 6 ) in the case of boron and phosphine (PH 3 ) gas in the case of phosphorus. In the following description, the case where these dopant gases are used will be described. Next, after purging these dopant gases, epitaxial growth is performed using SiH 4 gas as a raw material. The supply amount (growth recipe) of each gas is the same as that of oxygen gas. That is, during the growth of the silicon epitaxial layer, a dopant gas is introduced for a short time, that is, delta doping is performed.
　本法によることで、特許文献５ではビスマスに限定されていたドーパントの種類を拡張することが可能になる。 By this method, it becomes possible to expand the type of dopant limited to bismuth in Patent Document 5.
　以下、実施例及び比較例を示して本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
（実施例１）
　以下のようにして、図１に示す態様のエピタキシャルウェーハ１００を製造した。抵抗率１０Ω・ｃｍのボロンドープ、直径２００ｍｍのシリコン基板１０を材料として、まず、第１のエピタキシャル成長を行った（シリコンエピタキシャル層２１）。シリコン原料ガスはＳｉＨ４として５５０℃で成長を行った。膜厚に応じてシリコン原料ガスを流す時間を設定するが、成長レートは遅い方がよいため、０．０５ｎｍ／秒とし、シリコンエピタキシャル層２１の厚さは１０ｎｍとした。次に酸素ガス１０Ｌ／分を１×１０－８Ｔｏｒｒで３６０秒の時間だけリアクタに導入し、酸素原子層３１をおよそ５ｎｍ成長させた。次に、また第１のシリコンエピタキシャル層２１と同じ条件でシリコン原料ガスを導入し第２のシリコンエピタキシャル層２２の一部を１０ｎｍ形成した。 (Example 1)
The epitaxial wafer 100 of the aspect shown in FIG. 1 was manufactured as follows. First, a first epitaxial growth was performed using a silicon substrate 10 having a resistivity of 10 Ω · cm and boron doping and a diameter of 200 mm (silicon epitaxial layer 21). The silicon source gas was grown as SiH 4 at 550 ° C. Although the time for flowing the silicon source gas is set according to the film thickness, since the slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the silicon epitaxial layer 21 is set to 10 nm. Next, 10 L / min of oxygen gas was introduced into the reactor at 1 × 10 −8 Torr for a time of 360 seconds, and the oxygen atomic layer 31 was grown to approximately 5 nm. Next, a silicon source gas was introduced under the same conditions as those for the first silicon epitaxial layer 21 to form a part of the second silicon epitaxial layer 22 with a thickness of 10 nm.
　こののち、温度を６００℃に上げて成長速度を大きくして３μｍのシリコンエピタキシャル層を成長させて、エピタキシャル層５０中に酸素原子層３１を有するエピタキシャルウェーハ１００を製造した。 Thereafter, the temperature was raised to 600 ° C. to increase the growth rate to grow a 3 μm silicon epitaxial layer, and an epitaxial wafer 100 having an oxygen atomic layer 31 in the epitaxial layer 50 was manufactured.
（実施例２）
　以下のようにして、図２に示す態様のエピタキシャルウェーハ２００を製造した。抵抗率１０Ω・ｃｍのボロンドープ、直径２００ｍｍのシリコン基板１０を材料として、まず、第１のエピタキシャル成長を行った（シリコンエピタキシャル層２１）。シリコン原料ガスはＳｉＨ４として５５０℃で成長を行った。膜厚に応じてシリコン原料ガスを流す時間を設定するが、成長レートは遅い方がよいため、０．０５ｎｍ／秒とし、第１のシリコンエピタキシャル層２１の厚さは１０ｎｍとした。次に酸素ガス６Ｌ／分を１×１０－８Ｔｏｒｒで１００秒の時間だけリアクタに導入し、酸素原子層３１を１原子層成長させた。また第１のシリコンエピタキシャル層２１と同じ条件でシリコン原料ガスを導入し第２のシリコンエピタキシャル層２２を１０ｎｍ形成した。 (Example 2)
The epitaxial wafer 200 of the aspect shown in FIG. 2 was manufactured as follows. First, a first epitaxial growth was performed using a silicon substrate 10 having a resistivity of 10 Ω · cm and boron doping and a diameter of 200 mm (silicon epitaxial layer 21). The silicon source gas was grown as SiH 4 at 550 ° C. Although the time for flowing the silicon source gas is set in accordance with the film thickness, since a slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the first silicon epitaxial layer 21 is set to 10 nm. Next, oxygen gas 6 L / min was introduced into the reactor at 1 × 10 −8 Torr for 100 seconds to grow the oxygen atomic layer 31 by one atomic layer. A silicon source gas was introduced under the same conditions as those for the first silicon epitaxial layer 21 to form a second silicon epitaxial layer 22 having a thickness of 10 nm.
　さらに、酸素原子層３１と同じ条件で第２のシリコンエピタキシャル層２２の上に酸素原子層３２を堆積し、さらに第１のシリコンエピタキシャル層２１と同じ条件で第３のシリコンエピタキシャル層２３を堆積した上に、同条件で酸素原子層（３３、３４、３５）とシリコンエピタキシャル層（２４、２５、２６）を交互に堆積することで、酸素原子層／シリコンエピタキシャル層が５層の組４０を有するエピタキシャル層６０を含むエピタキシャルウェーハ２００を製造した。 Further, an oxygen atomic layer 32 was deposited on the second silicon epitaxial layer 22 under the same conditions as the oxygen atomic layer 31, and a third silicon epitaxial layer 23 was further deposited under the same conditions as the first silicon epitaxial layer 21. On top of this, oxygen atom layers (33, 34, 35) and silicon epitaxial layers (24, 25, 26) are alternately deposited under the same conditions, so that the oxygen atom layer / silicon epitaxial layer has a set 40 of five layers. An epitaxial wafer 200 including the epitaxial layer 60 was manufactured.
　最後の成長後に３μｍのエピタキシャル層２６の一部として、ＳｉＨ２Ｃｌ２を原料として成長させた。実際のデバイスを作製する活性領域として素子の種類にもよるがたいてい１μｍ程度の拡散領域が形成されることがあるため、この厚さとした。 After the final growth, SiH 2 Cl 2 was grown as a part of the 3 μm epitaxial layer 26 as a raw material. Depending on the type of element, a diffusion region of about 1 μm may be formed as an active region for manufacturing an actual device.
（比較例１）
　抵抗率１０Ω・ｃｍのボロンドープ、直径２００ｍｍシリコン基板を材料として、第１のエピタキシャル成長を行った。原料ガスはＳｉＨ４として５５０℃で成長を行った。膜厚に応じてシリコン原料ガスを流す時間を設定するが、成長レートは遅い方がよいため、０．０５ｎｍ／秒とし、シリコンエピタキシャル層の厚さは１０ｎｍとした。次に酸素１０Ｌ／分を　１×１０－８Ｔｏｒｒで７２０秒の時間だけリアクタに導入し、酸素原子層を１０ｎｍ成長させた。次に、また第１のエピタキシャル層と同じ条件でシリコン原料ガスを導入し第２のエピタキシャル層を形成しようとしたが、酸素原子層が厚くなっており、エピタキシャル成長が出来ず、多結晶シリコンとなった。このように酸素原子層が厚いと第２のシリコンエピタキシャル層が単結晶にならないことがわかる。 (Comparative Example 1)
First epitaxial growth was performed using a boron-doped, 200 mm diameter silicon substrate having a resistivity of 10 Ω · cm as a material. The source gas was grown as SiH 4 at 550 ° C. Although the time for flowing the silicon source gas is set according to the film thickness, since a slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the silicon epitaxial layer is set to 10 nm. Next, 10 L / min of oxygen was introduced into the reactor at 1 × 10 −8 Torr for a period of 720 seconds to grow an oxygen atomic layer by 10 nm. Next, the silicon source gas was introduced under the same conditions as the first epitaxial layer to try to form the second epitaxial layer. However, the oxygen atomic layer was thick, and epitaxial growth was not possible, resulting in polycrystalline silicon. It was. Thus, it can be seen that when the oxygen atomic layer is thick, the second silicon epitaxial layer does not become a single crystal.
（比較例２）
　抵抗率１０Ω・ｃｍのボロンドープ、直径２００ｍｍのシリコン基板を材料として、第１のエピタキシャル成長を行った。原料ガスはＳｉＨ２Ｃｌ２として１１００℃で成長を行った。膜厚に応じてシリコン原料ガスを流す時間を設定するが、成長レートは遅い方がよいため、０．０５ｎｍ／秒とし、シリコンエピタキシャル層の厚さは１０ｎｍとした。次に酸素１０Ｌ／分を１×１０－８Ｔｏｒｒで１００秒の時間だけリアクタに導入し、酸素原子層を１層成長させた。次に、また第１のエピタキシャル層と同じ条件でシリコン原料ガスを導入し第２のエピタキシャル層を形成しようとしたが、原料ガスに塩素が含まれており、酸素原子層がエッチングされて消失してしまった。 (Comparative Example 2)
First epitaxial growth was performed using a boron-doped, 200 mm-diameter silicon substrate having a resistivity of 10 Ω · cm as a material. The source gas was grown as SiH 2 Cl 2 at 1100 ° C. Although the time for flowing the silicon source gas is set according to the film thickness, since a slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the silicon epitaxial layer is set to 10 nm. Next, 10 L / min of oxygen was introduced into the reactor at 1 × 10 −8 Torr for a time of 100 seconds to grow one oxygen atom layer. Next, a silicon source gas was introduced under the same conditions as the first epitaxial layer to form a second epitaxial layer. However, the source gas contained chlorine, and the oxygen atomic layer was etched and disappeared. I have.
（実施例３）
　以下のようにして、図１に示す態様のエピタキシャルウェーハ１００であって、原子層として炭素原子層３１をエピタキシャル層中に有するものを製造した。抵抗率１０Ω・ｃｍのボロンドープ、直径２００ｍｍのシリコン基板１０を材料として、まず、第１のエピタキシャル成長を行った（シリコンエピタキシャル層２１）。シリコン原料ガスはＳｉＨ４として５５０℃で成長を行った。膜厚に応じてシリコン原料ガスを流す時間を設定するが、成長レートは遅い方がよいため、０．０５ｎｍ／秒とし、シリコンエピタキシャル層２１の厚さは１０ｎｍとした。次にＣＨ４ガス１０Ｌ／分を１×１０－８Ｔｏｒｒで３６０秒の時間だけリアクタに導入し、炭素原子層３１をおよそ２ｎｍ成長させた。次に、また第１のシリコンエピタキシャル層２１と同じ条件でシリコン原料ガスを導入し第２のシリコンエピタキシャル層２２の一部を１０ｎｍ形成した。 (Example 3)
The epitaxial wafer 100 having the aspect shown in FIG. 1 and having the carbon atom layer 31 as an atomic layer in the epitaxial layer was manufactured as follows. First, a first epitaxial growth was performed using a silicon substrate 10 having a resistivity of 10 Ω · cm and boron doping and a diameter of 200 mm (silicon epitaxial layer 21). The silicon source gas was grown as SiH 4 at 550 ° C. Although the time for flowing the silicon source gas is set according to the film thickness, since the slower growth rate is better, it is set to 0.05 nm / second, and the thickness of the silicon epitaxial layer 21 is set to 10 nm. Next, 10 L / min of CH 4 gas was introduced into the reactor at 1 × 10 −8 Torr for a time of 360 seconds, and the carbon atom layer 31 was grown to approximately 2 nm. Next, a silicon source gas was introduced under the same conditions as those for the first silicon epitaxial layer 21 to form a part of the second silicon epitaxial layer 22 with a thickness of 10 nm.
　こののち、温度を６００℃に上げて成長速度を大きくして３μｍのシリコンエピタキシャル層を成長させて、エピタキシャル層５０中に炭素原子層３１を有するエピタキシャルウェーハ１００を製造した。 Thereafter, the temperature was raised to 600 ° C. to increase the growth rate, and a 3 μm-thick silicon epitaxial layer was grown to manufacture an epitaxial wafer 100 having the carbon atom layer 31 in the epitaxial layer 50.
　なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は、例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 Note that 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.

Claims (6)

  1. 　シリコン基板上にエピタキシャル層を形成するエピタキシャルウェーハの製造方法であって、
    　前記エピタキシャル層中に、酸素、炭素、窒素、ゲルマニウム、スズ、ホウ素及びリンからなる群から選ばれる１種の元素の原子からなり、厚さが５ｎｍ以下である原子層を形成する工程を有し、
    　前記原子層に接するエピタキシャル層の形成を、ＳｉＨ４ガスを用いて行うことを特徴とするエピタキシャルウェーハの製造方法。     An epitaxial wafer manufacturing method for forming an epitaxial layer on a silicon substrate,
    A step of forming an atomic layer made of atoms of one element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron, and phosphorus and having a thickness of 5 nm or less in the epitaxial layer; ,
    An epitaxial wafer manufacturing method comprising forming an epitaxial layer in contact with the atomic layer by using SiH 4 gas.
  2. 　前記原子層を、１原子層として形成することを特徴とする請求項１に記載のエピタキシャルウェーハの製造方法。 The method for producing an epitaxial wafer according to claim 1, wherein the atomic layer is formed as a single atomic layer.
  3. 　前記エピタキシャル層の領域のうち、前記原子層に接し、少なくとも該原子層から５ｎｍまでの領域を、ＳｉＨ４ガスを用いて形成することを特徴とする請求項１又は請求項２に記載のエピタキシャルウェーハの製造方法。 3. The epitaxial wafer according to claim 1, wherein, in the region of the epitaxial layer, a region that is in contact with the atomic layer and is at least 5 nm from the atomic layer is formed using SiH 4 gas. 4. Manufacturing method.
  4. 　前記原子層を、前記エピタキシャル層中に複数層形成することを特徴とする請求項１から請求項３のいずれか１項に記載のエピタキシャルウェーハの製造方法。 The method for producing an epitaxial wafer according to any one of claims 1 to 3, wherein a plurality of the atomic layers are formed in the epitaxial layer.
  5. 　前記エピタキシャル層の領域のうち、前記ＳｉＨ４ガスを用いて形成する領域以外の領域を、ＳｉＨ２Ｃｌ２ガス又はＳｉＨＣｌ３ガスを用いて形成することを特徴とする請求項１から請求項４のいずれか１項に記載のエピタキシャルウェーハの製造方法。 The region of the epitaxial layer other than the region formed using the SiH 4 gas is formed using a SiH 2 Cl 2 gas or a SiHCl 3 gas. The manufacturing method of the epitaxial wafer of any one of Claims.
  6. 　前記原子層の形成を、
    　酸素原子層を形成する場合は酸素ガスを、
    　炭素原子層を形成する場合はＣＨ４ガスを、
    　窒素原子層を形成する場合はＮＨ３ガスを、
    　ゲルマニウム原子層を形成する場合はＧｅを含む有機金属ガスを、
    　スズ原子層を形成する場合はＳｎを含む有機金属ガスを、
    　ホウ素原子層を形成する場合はＢ２Ｈ６ガスを、
    　リン原子層を形成する場合はＰＨ３ガスを、
    　用いて行うことを特徴とする請求項１から請求項５のいずれか１項に記載のエピタキシャルウェーハの製造方法。     Forming the atomic layer,
    When forming an oxygen atomic layer, oxygen gas,
    When forming a carbon atomic layer, CH 4 gas is used.
    When forming a nitrogen atom layer, NH 3 gas is used.
    In the case of forming a germanium atomic layer, an organometallic gas containing Ge is used.
    In the case of forming a tin atomic layer, an organometallic gas containing Sn is used.
    In the case of forming a boron atomic layer, B 2 H 6 gas is used.
    When forming a phosphorus atomic layer, PH 3 gas is used.
    The method for producing an epitaxial wafer according to any one of claims 1 to 5, wherein the method is performed.
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