CN110678964A - Method for manufacturing epitaxial wafer - Google Patents

Method for manufacturing epitaxial wafer Download PDF

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Publication number
CN110678964A
CN110678964A CN201880034863.7A CN201880034863A CN110678964A CN 110678964 A CN110678964 A CN 110678964A CN 201880034863 A CN201880034863 A CN 201880034863A CN 110678964 A CN110678964 A CN 110678964A
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layer
epitaxial
gas
silicon
forming
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大槻刚
水泽康
铃木克佳
石崎顺也
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Shin Etsu Handotai Co Ltd
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Shin Etsu Handotai Co Ltd
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Abstract

The present invention provides a method for manufacturing an epitaxial wafer, which forms an epitaxial layer on a silicon substrate, and which has a step of forming an atomic layer in the epitaxial layer, wherein the atomic layer is formed by atoms of one element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus, has a thickness of 5nm or less, and uses SiH4Gas forming an epitaxial layer in contact with the atomic layer. Thus, a method for manufacturing an epitaxial wafer can be provided, in which an atomic layer of oxygen or the like can be stably introduced into an epitaxial layer.

Description

Method for manufacturing epitaxial wafer
Technical Field
The invention relates to a method for manufacturing an epitaxial wafer.
Background
A silicon substrate on which a solid-state image sensor or other semiconductor elements such as transistors are formed is required to have a function of gettering elements such as heavy metals which impair element characteristics. For gettering, various methods of forming a polycrystalline silicon (Poly-Si) layer on the back surface of a silicon substrate and forming a scratch layer by shot peening, or forming precipitates by using high boron concentration in a silicon substrate have been proposed and put into practical use. Regarding gettering by oxygen precipitation, for oxygen having a large electronegativity, gettering is performed by capturing a metal having a large ionization tendency (having a small electronegativity).
Furthermore, it has been proposed to form a gettering layer, so-called neighbor gettering, near the active region of the element. For example, there are substrates in which silicon is epitaxially grown on a substrate in which carbon is ion-implanted. Gettering requires diffusion of the element to the gettering site (metals are more prone to binding or segregation at the site than are present as single elements, thereby reducing the energy of the overall system). The diffusion coefficient of the metal element contained in silicon differs depending on the element, and a method of close proximity gettering has been proposed in consideration of the fact that the metal cannot diffuse to the gettering site due to the recent process low temperature.
It is considered that if oxygen can be used for the gettering in the vicinity, a silicon substrate having a very effective gettering layer can be obtained. In particular, in the case of an epitaxial wafer having an oxygen atomic layer in the middle of the epitaxial layer, even in a recent low-temperature process, it is possible to reliably remove the metal impurities.
As described above, the gettering of metal impurities is mainly performed, and for example, as an effect of oxygen, an effect of preventing autodoping at the time of epitaxial growth by forming a CVD oxide film on the back surface is known.
Further, in addition to oxygen, the following various effects by combinations of silicon and other elements can be expected and applied: carbon of group IV (group 14) as silicon has a gettering effect by carbon; use of a combination of Ge and a silicon oxide film in an optical device; surface modification effects of Sn when Ge or the like is grown on silicon; and when the component is other than group IV, the strength is improved by the promotion of the precipitation of nitrogen.
The prior art will be explained. Patent document 1 is a method of forming a structure of a thin layer of oxygen on silicon and further growing the silicon. The method is a technology based on ALD ("Atomic layer deposition"). ALD is a method of adsorbing molecules containing target atoms and then desorbing and removing unnecessary atoms (molecules) in the molecules, and is widely used because of its extremely high precision and good reaction controllability by using surface bonding, but has disadvantages as follows: impurities that are not needed for atomic layer formation and exhibit unintended characteristics are generated due to the removal of unnecessary atoms. Actually, in the ALD method, since a carbon-containing molecule is used to form an oxygen layer, there is a possibility that an influence of carbon (unnecessary carbon) is present.
Patent document 2 is a technique relating to a reactor for realizing the same substrate as patent document 1, and regarding the raw material gas and the method, MOVPE (metal organic chemical vapor deposition) is set. Since it is MOVPE, organic metal is used. Although reaction control is easy, there may be an unnecessary impurity metal in forming the oxygen atom layer. Particularly when applied to the silicon substrate itself, there may be metal contamination.
As described above, the techniques of patent documents 1 and 2 are based on various techniques such as ALD and MOVPE.
Patent documents 3 and 4 show that improvement of device characteristics (mobility) can be improved by introducing a plurality of atomic oxygen layers on a silicon substrate, but a specific growth method is not mentioned.
As a conventional technique for introducing an atomic layer other than oxygen into a silicon substrate, for example, as described in patent document 5, a method of forming a steep bismuth distribution (profile) on the surface of silicon is disclosed. Patent document 5 describes Delta doping and discloses a basic technique of embedding a dopant in a linear shape, but it is considered that it is difficult to spread the entire surface of the wafer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2014-165494
Patent document 2: japanese laid-open patent publication No. 2013-197291
Patent document 3: U.S. Pat. No. 7,153,763
Patent document 4: specification of U.S. Pat. No. 7,265,002
Patent document 5: japanese laid-open patent publication No. 2000-003877
Disclosure of Invention
Technical problem to be solved by the invention
In view of the above problems, an object of the present invention is to provide a method for manufacturing an epitaxial wafer, which can stably introduce an atomic layer of oxygen or the like into an epitaxial layer.
Means for solving the problems
In order to achieve the above object, the present invention provides a method for manufacturing an epitaxial wafer, which includes forming an epitaxial layer on a silicon substrate, the method including a step of forming an atomic layer in the epitaxial layer, the atomic layer being formed of atoms of one element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron, and phosphorus, the atomic layer having a thickness of 5nm or less, and using SiH4And a gas forming an epitaxial layer in contact with the atomic layer.
In the method for manufacturing an epitaxial wafer, an atomic layer formed of atoms of an element such as oxygen can be stably formed in the epitaxial layer. In particular, the use of SiH having no chlorine atom in the molecule4Gas, formed into atomic form with elements such as oxygenSince the epitaxial layer is in contact with the formed atomic layer, etching of the atomic layer such as oxygen can be prevented.
In the method for manufacturing an epitaxial wafer according to the present invention, the atomic layer may be a monoatomic layer.
In the present invention, as described above, an atomic layer of oxygen or the like can be formed as a monoatomic layer. Further, when such a monoatomic layer is to be formed, according to the method of the present invention, the monoatomic layer can be stably formed.
Furthermore, SiH is preferably used4And a gas forming a region of the epitaxial layer which is contiguous to the atomic layer and which is at least 5nm from the atomic layer.
Thus, by using SiH containing no chlorine4And a gas starting from the atomic layer of oxygen and the like to a region of at least 5nm in a region where the epitaxial layer is formed, whereby the atomic layer of oxygen and the like can be formed more stably.
Further, a plurality of the atomic layers can be formed in the epitaxial layer.
In the present invention, a plurality of atomic layers of oxygen or the like can be formed in the epitaxial layer. Further, the structure can be stably formed.
Furthermore, SiH is preferably used2Cl2Gas or SiHCl3A gas in a region where the epitaxial layer is formed except for the SiH4The region other than the region where the gas is formed.
Thus, by using SiH2Cl2Gas or SiHCl3Gas, except for SiH in forming epitaxial layer4The region other than the region where the gas is formed can be a region apart from the atomic layer of oxygen or the like to form a thick epitaxial layer. As a result, the entire epitaxial layer can be formed in a shorter time, which contributes to productivity and cost.
Further, in the case of forming an oxygen atom layer, the atom layer may be formed using oxygen gas; in the case of forming a carbon atom layer, CH may be used4A gas forming the atomic layer; in the case of forming a nitrogen atom layer, NH may be used3A gas forming the atomic layer; in the case of forming an atomic layer of germaniumThe atomic layer may be formed using an organometallic gas containing Ge; in the case of forming a tin atomic layer, the atomic layer may be formed using an organometallic gas containing Sn; in the case of forming a boron atomic layer, B may be used2H6A gas forming the atomic layer; in the case of forming a phosphorus atom layer, pH may be used3A gas forming the atomic layer.
By using these gases, an atomic layer of oxygen or the like can be formed.
Effects of the invention
According to the present invention, in a silicon epitaxial wafer used for a front-edge device, an atomic layer of oxygen or the like can be stably introduced into an epitaxial layer. Further, a proximity gettering substrate having a proximity gettering effect by an oxygen atom layer or a functional substrate having a composite function using a group IV element, nitrogen, a dopant, or the like can be manufactured.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of an epitaxial wafer having an atomic layer of oxygen and the like, which can be produced by the present invention.
Fig. 2 is a schematic cross-sectional view showing an example of an epitaxial wafer having a plurality of atomic layers of oxygen and the like, which can be produced by the present invention.
Fig. 3 is a conceptual diagram of growth dosing for manufacturing an epitaxial wafer of the present invention.
Detailed Description
The present invention will be described in detail with reference to the drawings, but the present invention is not limited thereto.
The present invention is a method for manufacturing an epitaxial wafer having an epitaxial layer formed on a silicon substrate, the method including a step of forming an atomic layer in the epitaxial layer, the atomic layer being formed of atoms of one element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron, and phosphorus, and having a thickness of 5nm or less. In the present invention, SiH is further used4And forming an epitaxial layer in contact with the atomic layer. In the following description, atoms of one element of oxygen, carbon, nitrogen, germanium, tin, boron, and phosphorus to be formed in the epitaxial layerThe formed atomic layer is simply referred to as an "atomic layer".
[ case of introducing oxygen atom layer into epitaxial layer ]
First, a case where an oxygen atomic layer is introduced into an epitaxial layer on a silicon substrate will be described.
Fig. 1 shows a schematic cross-sectional view of an epitaxial wafer 100 having an oxygen atom layer, which can be produced by the method for producing an epitaxial wafer of the present invention. The epitaxial wafer 100 has an epitaxial layer 50 formed on a silicon substrate 10, and an atomic layer (oxygen atomic layer) 31 formed of oxygen atoms and having a thickness of 5nm 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 atom layer 31. An oxygen atom layer 31 is formed on the silicon epitaxial layer 21, and a silicon epitaxial layer 22 is formed on the oxygen atom layer 31. In the example of fig. 1, an epitaxial layer 50 formed of a silicon epitaxial layer 21, an oxygen atom layer 31, and a silicon epitaxial layer 22 is formed.
As described above, the following method is used as a manufacturing method for forming the oxygen atom layer 31. Epitaxial growth is performed on the silicon substrate 10, and first, a silicon epitaxial layer 21 is formed. An oxygen atom layer 31 is grown on the silicon epitaxial layer 21. Further, silicon is epitaxially grown on the oxygen atom layer 31 to form a silicon epitaxial layer 22. Thereby, the entire epitaxial layer 50 having the oxygen atom layer 31 is formed, and the epitaxial wafer 100 is formed.
In fig. 1, the oxygen atom layer is a single layer, but a plurality of oxygen atom layers may be formed by repeating the oxygen atom layer and silicon epitaxial growth. Fig. 2 shows an epitaxial wafer having a plurality of oxygen atom layers formed in the epitaxial layer. That is, when manufacturing the epitaxial wafer 200 shown in fig. 2, the manufacturing can be performed in the following manner. First, a silicon epitaxial layer 21 is formed on a silicon substrate 10. An oxygen atom layer 31 is formed on the silicon epitaxial layer 21. Further, a silicon epitaxial layer 22 is formed on the oxygen atom layer 31. In the embodiment of fig. 2, the atomic oxygen layer 32, the silicon epitaxial layer 23, the atomic oxygen layer 33, the silicon epitaxial layer 24, the atomic oxygen layer 34, the silicon epitaxial layer 25, the atomic oxygen layer 35, and the silicon epitaxial layer 26 are further formed, similarly to the embodiment of fig. 1. Thereby, an epitaxial layer 60 can be formed, and the epitaxial layer 60 is formed with the structure 40 in which 5 sets of silicon epitaxial layers and oxygen atom layers are repeated. By forming a plurality of oxygen atom layers in this manner, an epitaxial wafer having a more excellent gettering effect can be obtained. At this time, it is sufficient that the oxygen atom layer is 10 layers at the maximum.
In the present invention, SiH containing no chlorine atom is used as a raw material for silicon epitaxial growth in forming an epitaxial layer in contact with an atomic layer4A gas. This is because, when the gas for epitaxial growth contains chlorine atoms, the chlorine atoms etch even when an oxygen atom layer is formed.
Further, the oxygen atom layer needs to be made 5nm or less, and is preferably as thin as possible, and an amount of the degree of the adsorption monoatomic layer is preferably introduced. If the oxygen atomic layer is thicker than 5nm, the silicon layer is oxidized and the second silicon epitaxial layer cannot be deposited on the oxygen atomic layer. To be precise, even when silicon is epitaxially grown on such an oxygen atom layer, the silicon is not epitaxially grown but is converted into amorphous silicon or polycrystallized (polymerized).
The oxygen atom layer may be formed by depositing one Langmuir (Langmuir) layer using the principle of isothermal adsorption. One langmuir layer can be deposited if one is skilled in the art. Although it is related to the size of the furnace chamber, it can be solved by flowing oxygen at about 10L/min (for example, 5L/min to 15L/min). Further, for example, the conditions of pressure and time may be set to 1 × 10-8Torr(1.33×10-6Pa) and about 100 seconds, but this is not a requirement and may be 1 × 10-61 × 10 above Torr -910 to 500 seconds below Torr. The temperature may be set to a range not exceeding the epitaxial growth temperature. The growth rate is preferably 0.005 nm/sec or less.
The method for manufacturing an epitaxial wafer will be described in more detail with reference to the embodiment of fig. 1. In order to introduce the oxygen atom layer 31 into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, SiH containing no chlorine is first used4The gas is used as a source gas for epitaxial growth to form the silicon epitaxial layer 21. SiH is preferably introduced from a position at least 5nm away from the position where the oxygen atom layer 31 is formed4The gas is used as a source gas, and the silicon epitaxial layer 21 is grown using a gas not containing chlorine. In the case of SiH purging4After the gas is introduced, oxygen gas is introduced to grow an oxygen atom layer 31 having a thickness of 5nm or less. Then, after cleaningAfter oxygen, SiH4The gas is used as a raw material, and epitaxial growth is performed to a desired thickness. It is preferable to introduce SiH at a position at least 5nm away from the position where the oxygen atom layer 31 is formed4The gas is used as a source gas, and the silicon epitaxial layer 22 is grown using a gas not containing chlorine. Fig. 3 shows a supply image of each gas.
As described above, the oxygen atom layer is preferably formed as a monoatomic layer. By setting the introduction of oxygen to a condition in which one langmuir (isothermal monatomic adsorption) amount is introduced so that oxygen is adsorbed as a monoatomic layer, oxygen monoatomic growth (Delta doping) can be achieved.
In the case of forming an epitaxial layer in contact with an oxygen atom layer, a gas containing chlorine (chlorine atom) (e.g., SiH) is used2Cl2Gas or SiHCl3Chlorosilanes such as gas), the oxygen layer deposited in the silicon disappears due to the etching effect by chlorine. Therefore, SiH is required to be used4The gas forms an epitaxial layer in contact with the atomic layer of oxygen 31. Particular preference is given to using SiH4And a gas in a region starting from the oxygen atom layer 31 to at least 5nm (a region starting from the oxygen atom layer 31 to 5nm in the silicon epitaxial layers 21 and 22) in contact with the oxygen atom layer 31 in the region where the epitaxial layer 50 is formed. Since the oxygen atom layer 31 is not in direct contact with the chlorine-containing gas, the oxygen atom layer 31 can be prevented from being etched by the chlorine gas.
That is, to prevent the etching of the oxygen atom layer 31 of fig. 1, SiH is used only4Instead of forming an epitaxial layer in contact with the oxygen atom layer 31, SiH may be used2Cl2Gas or SiHCl3Gas, except for SiH in the region where epitaxial layer is formed4The region other than the region where the gas is formed. Especially if SiH is used4The gas formation is started from the atomic oxygen layer 31 to at least 5nm, the atomic oxygen layer 31 is completely SiH4Capping, therefore, for epitaxial layers forming regions more than 5nm from the oxygen atom layer, not limited to SiH containing no chlorine gas4SiH may also be used2Cl2Or SiHCl3. By using SiH in forming a thicker epitaxial layer in a region far from the oxygen atom layer2Cl2Or SiHCl3Can be used forAn epitaxial layer is formed in a short time. Due to the use of SiH4Since the growth rate is slow in the case of gas, for example, when an epitaxial layer having a thickness of 100nm or more is formed, it is preferable to substitute SiH in the middle of the formation2Cl2Or SiHCl3. This enables high productivity and low cost. The growth temperature of the silicon epitaxial layer is preferably in the range of 500 ℃ to 800 ℃.
In the same manner as in fig. 2, SiH is required to be used for all of the oxygen atomic layers 31, 32, 33, 34, and 354The gas forms an epitaxial layer in contact with the oxygen atom layer 31, and preferably a region of 5nm from the oxygen atom layer is subjected to SiH4And (4) epitaxial growth of gas.
In the silicon epitaxial wafer having an oxygen atom layer produced by the method of the present invention, a neighbor gettering effect can be expected, and an improvement in device yield can also be expected.
[ case of introducing a carbon atom layer into an epitaxial layer ]
Next, a case of introducing a carbon atomic layer into an epitaxial layer on a silicon substrate will be described. Since the oxygen atom layer is basically the same as the case of introducing the oxygen atom layer, the overlapping description is omitted.
The epitaxial wafer 100 having the epitaxial layer 50 including an oxygen atom layer is the same as the epitaxial wafer 100 described above except that the atomic layer 31 is formed using a carbon atom layer instead of an oxygen atom layer when introducing the carbon atom layer to the epitaxial wafer 100.
In this method, since the carbon atomic layer 31 is introduced into the silicon substrate 10, when the epitaxial growth is performed on the silicon substrate 10, SiH containing no chlorine is used first4The gas is used as a source gas for epitaxial growth to form the silicon epitaxial layer 21. In the case of SiH purging4After the gas is introduced, a gas containing carbon atoms instead of chlorine atoms is introduced to grow a carbon atom layer 31 having a thickness of 5nm or less. As the gas, CH is particularly preferable4Gas (methane gas). In the following description, CH is used4The case of gas will be described. Then, in clearing CH4After the gas is treated with SiH4And (4) epitaxial growth with gas as a raw material. The amount of each gas supplied (growth dose) was the same as in the case of oxygen. That is to say that the first and second electrodes,introducing CH for a short time during the growth of the silicon epitaxial layer4Gas, Delta doping is performed.
In the silicon epitaxial wafer having a carbon atom layer manufactured by the method of the present invention, a neighbor gettering effect can be expected, and improvement of the device yield can be expected. Further, since carbon has a smaller atomic radius than silicon, it has an effect of deforming a silicon layer grown on a carbon atomic layer, and can be expected to improve carrier mobility (carrier mobility) of the device.
[ case of introducing a Nitrogen atom layer into an epitaxial layer ]
Next, a case of introducing a nitrogen atomic layer into an epitaxial layer on a silicon substrate will be described. Since the oxygen atom layer is basically the same as the case of introducing the oxygen atom layer, the overlapping description is omitted.
The epitaxial wafer 100 having the epitaxial layer 50 including an oxygen atom layer is the same as the epitaxial wafer 100 described above except that the atomic layer 31 is formed using a nitrogen atom layer instead of an oxygen atom layer when introducing the nitrogen atom layer to the epitaxial wafer 100.
In this method, since the nitrogen atom layer 31 is introduced into the silicon substrate 10, when the epitaxial growth is performed on the silicon substrate 10, SiH containing no chlorine is used first4The gas is used as a source gas for epitaxial growth to form the silicon epitaxial layer 21. In the case of SiH purging4After the gas is introduced, a gas containing nitrogen atoms instead of chlorine atoms is introduced, and a nitrogen atom layer 31 having a thickness of 5nm or less is grown. The gas is particularly preferably NH3Gas (ammonia). In the following description, NH is used3The case of gas will be described. Then, NH is purged3After the gas is treated with SiH4And (4) epitaxial growth with gas as a raw material. The amount of each gas supplied (growth dose) was the same as in the case of oxygen. That is, NH is introduced for a short time during the growth of the silicon epitaxial layer3Gas, Delta doping is performed.
This makes it possible to obtain an epitaxial wafer in which oxygen precipitation by nitrogen is promoted and the strength of the silicon substrate is improved. At this time, a maximum of 10 nitrogen atom layers is sufficient. By the nitrogen atomic layer, an effect of preventing the grown silicon layer from slipping on the atomic layer can be expected.
[ case of introducing germanium atomic layer into epitaxial layer ]
Next, a case where a germanium atomic layer is introduced into an epitaxial layer on a silicon substrate will be described. Since the oxygen atom layer is basically the same as the case of introducing the oxygen atom layer, the overlapping description is omitted.
The epitaxial wafer 100 having the epitaxial layer 50 including an oxygen atom layer is the same as the epitaxial wafer 100 described above except that the atomic layer 31 is formed using a germanium atom layer instead of the oxygen atom layer when introducing the germanium atom layer to the epitaxial wafer 100.
In this method, since the germanium atom layer 31 is introduced into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, SiH containing no chlorine is first used4The gas is used as a source gas for epitaxial growth to form the silicon epitaxial layer 21. In the case of SiH purging4After the gas is introduced, a gas containing germanium atoms instead of chlorine atoms is introduced to grow a germanium atom layer 31 having a thickness of 5nm or less. The gas is particularly preferably an organometallic gas containing germanium (tetramethylgermanium or the like). In the following description, a case of using a tetramethylgermanium gas will be described. Then, after removing the tetramethylgermanium gas, SiH is performed4And (4) epitaxial growth with gas as a raw material. The amount of each gas supplied (growth dose) was the same as in the case of oxygen. That is, during the growth of the silicon epitaxial layer, the Delta doping is performed by introducing the tetramethylgermanium gas for a short time.
This makes it possible to obtain a substrate in which Ge and silicon are stacked. Then, by exposing the substrate to an oxidizing atmosphere, since silicon is more easily oxidized than Ge, Ge/SiO can be formed2/Ge/SiO2The laminated structure of (3) can be expected to be applied to a substrate for an optical device.
[ case of introducing a tin atomic layer into an epitaxial layer ]
Next, a case where a tin atomic layer is introduced into an epitaxial layer on a silicon substrate will be described. Since the oxygen atom layer is basically the same as the case of introducing the oxygen atom layer, the overlapping description is omitted.
The epitaxial wafer 100 having the epitaxial layer 50 including an oxygen atom layer is the same as the epitaxial wafer 100 described above except that a tin atom layer is used as the atomic layer 31 instead of the oxygen atom layer when introducing the tin atom layer on the epitaxial wafer 100.
In this method, since the tin atomic layer 31 is introduced into the silicon substrate 10, when the epitaxial growth is performed on the silicon substrate 10, SiH containing no chlorine is used first4The gas is used as a source gas for epitaxial growth to form the silicon epitaxial layer 21. In the case of SiH purging4After the gas is introduced, a gas containing tin atoms instead of chlorine atoms is introduced to grow a tin atom layer 31 having a thickness of 5nm or less. The gas is particularly preferably an organic metal gas containing tin (e.g., tetramethyltin). In the following description, a case of using tetramethyltin gas will be described. Then, after removing the tetramethyltin gas, SiH was added4And (4) epitaxial growth with gas as a raw material. The amount of each gas supplied (growth dose) was the same as in the case of oxygen. That is, during the growth of the silicon epitaxial layer, the Delta doping is performed by introducing tetramethyltin gas for a short time.
As a practical method of using Sn, it is considered to use it for surface modification in growing various elements including Ge on silicon. In this case, after Sn is grown by the method, Ge is grown by the same method.
[ case where boron atom layer or phosphorus atom layer is introduced into epitaxial layer ]
Next, a case where a boron atomic layer or a phosphorus atomic layer is introduced into an epitaxial layer on a silicon substrate will be described. Since the oxygen atom layer is basically the same as the case of introducing the oxygen atom layer, the overlapping description is omitted.
The epitaxial wafer 100 having the epitaxial layer 50 including an oxygen atom layer is the same as the epitaxial wafer 100 described above except that the atomic layer 31 is formed using a boron or phosphorus atom layer instead of an oxygen atom layer when introducing a boron or phosphorus atom layer to the epitaxial wafer 100.
In this method, since the boron atom layer 31 or the phosphorus atom layer 31 is introduced into the silicon substrate 10, when epitaxial growth is performed on the silicon substrate 10, SiH containing no chlorine is first used4The gas is used as a source gas for epitaxial growth to form the silicon epitaxial layer 21. In the case of SiH purging4Introducing a gas containing boron or phosphorus atoms without chlorine atoms to form a boron or phosphorus layer having a thickness of 5nm or less31 are grown. When boron is used as the gas, diborane (B) is particularly preferable2H6) Phosphorus, particularly preferably phosphine (pH)3) A gas. In the following description, the case of using these dopant gases will be described. Then, after removing these doping gases, SiH is performed4And (4) epitaxial growth with gas as a raw material. The amount of each gas supplied (growth dose) was the same as in the case of oxygen. That is, during the growth of the silicon epitaxial layer, Delta doping is performed by introducing a dopant gas for a short time.
By using this method, the kind of dopant limited to bismuth in patent document 5 can be expanded.
Examples
The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples.
(example 1)
The epitaxial wafer 100 of the form shown in fig. 1 is manufactured in the following manner. A silicon substrate 10 having a resistivity of 10 Ω · cm, which is doped with boron and has a diameter of 200mm, is used as a material, and first epitaxial growth (silicon epitaxial layer 21) is performed. Adding SiH4As a silicon source gas, growth was carried out at 550 ℃. The time for flowing the silicon source gas was set according to the film thickness, but the growth rate was preferably slow, and therefore the thickness of the silicon epitaxial layer 21 was set to 10nm at 0.05 nm/sec. Then, at 10L/min, 1X 10-8Oxygen gas was introduced into the reactor for 360 seconds under Torr to grow about 5nm in the oxygen atom layer 31. Then, a silicon source gas was introduced under the same conditions as those of the first silicon epitaxial layer 21 to form a 10nm portion of the second silicon epitaxial layer 22.
Then, the temperature was increased to 600 ℃, and a 3 μm silicon epitaxial layer was grown by increasing the growth rate, thereby producing an epitaxial wafer 100 having an oxygen atom layer 31 in the epitaxial layer 50.
(example 2)
The epitaxial wafer 200 of the form shown in fig. 2 was produced in the following manner. A silicon substrate 10 having a resistivity of 10 Ω · cm, which is doped with boron and has a diameter of 200mm, is used as a material, and first epitaxial growth (silicon epitaxial layer 21) is performed. Adding SiH4As a silicon raw material gas, 5The growth was carried out at 50 ℃. The time for flowing the silicon source gas was set according to the film thickness, but the growth rate was preferably slow, and therefore the thickness of the first silicon epitaxial layer 21 was set to be 10nm at 0.05 nm/sec. Then, at 6L/min, 1X 10-8Oxygen gas was introduced into the reactor for 100 seconds under Torr to grow an oxygen atom layer 31 as a monoatomic layer. Further, a silicon source gas was introduced under the same conditions as those of the first silicon epitaxial layer 21 to form a 10nm second silicon epitaxial layer 22.
Further, an oxygen atom layer 32 is deposited on the second silicon epitaxial layer 22 under the same conditions as the oxygen atom layer 31, further, a third silicon epitaxial layer 23 is deposited under the same conditions as the first silicon epitaxial layer 21, and oxygen atom layers (33, 34, 35) and silicon epitaxial layers (24, 25, 26) are alternately deposited under the same conditions, thereby manufacturing an epitaxial wafer 200 containing an epitaxial layer 60, the epitaxial layer 60 having a group 40 of 5 oxygen atom layers/silicon epitaxial layer.
After the final growth, with SiH2Cl2As a raw material, a 3 μm portion of the epitaxial layer 26 was grown. The active region used for fabricating an actual device depends on the type of the device, but is usually formed to have a thickness of about 1 μm since a diffusion region is often formed.
Comparative example 1
A silicon substrate having a resistivity of 10. omega. cm, which is doped with boron and has a diameter of 200mm, is used as a material, and first epitaxial growth is performed. Adding SiH4As a raw material gas, growth was carried out at 550 ℃. The time for flowing the silicon source gas was set according to the film thickness, but the growth rate was preferably slow, and therefore the thickness of the silicon epitaxial layer was set to 10nm at 0.05 nm/sec. Then, at 10L/min, 1X 10-8Oxygen gas was introduced into the reactor for 720 seconds at Torr to grow an oxygen atom layer at 10 nm. Then, when a silicon source gas is introduced under the same conditions as those of the first epitaxial layer to form a second epitaxial layer, the oxygen atom layer becomes thick and cannot be epitaxially grown, thereby forming polycrystalline silicon. As can be seen, if the oxygen atom layer is thick, the second silicon epitaxial layer cannot be formed into a single crystal.
Comparative example 2
A silicon substrate having a resistivity of 10. omega. cm, which was doped with boron and had a diameter of 200mm, was used as a materialAnd (6) first epitaxial growth. Adding SiH2Cl2As a raw material gas, growth was performed at 1100 ℃. The time for flowing the silicon source gas was set according to the film thickness, but the growth rate was preferably slow, and therefore the thickness of the silicon epitaxial layer was set to 10nm at 0.05 nm/sec. At 10L/min, 1X 10-8Oxygen gas was introduced into the reactor for 100 seconds under Torr to grow 1 layer of oxygen atomic layer. Then, when a silicon source gas is introduced under the same conditions as those of the first epitaxial layer to form a second epitaxial layer, chlorine is contained in the source gas, and the oxygen atom layer is etched and disappears.
(example 3)
An epitaxial wafer 100 having a carbon atom layer 31 as an atomic layer in an epitaxial layer in the form shown in fig. 1 was manufactured in the following manner. A silicon substrate 10 having a resistivity of 10 Ω · cm, which is doped with boron and has a diameter of 200mm, is used as a material, and first epitaxial growth (silicon epitaxial layer 21) is performed. Adding SiH4As a silicon source gas, growth was carried out at 550 ℃. The time for flowing the silicon source gas was set according to the film thickness, but the growth rate was preferably slow, and therefore the thickness of the silicon epitaxial layer 21 was set to 10nm at 0.05 nm/sec. Then, at 10L/min, 1X 10-8Torr, 360 seconds CH was introduced into the reactor4The gas grows the carbon atom layer 31 by about 2 nm. Then, a silicon source gas was introduced under the same conditions as those of the first silicon epitaxial layer 21 to form a 10nm portion of the second silicon epitaxial layer 22.
Then, the temperature was increased to 600 ℃, the growth rate was increased, and a 3 μm silicon epitaxial layer was grown, thereby producing an epitaxial wafer 100 having a carbon atom layer 31 in the epitaxial layer 50.
The present invention is not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.

Claims (6)

1. A method for manufacturing an epitaxial wafer, which forms an epitaxial layer on a silicon substrate,
the epitaxial layer is formed with an atomic layer which is formed by atoms of one element selected from the group consisting of oxygen, carbon, nitrogen, germanium, tin, boron and phosphorus and has a thickness of 5nm or less,
using SiH4And a gas forming an epitaxial layer in contact with the atomic layer.
2. The method for manufacturing an epitaxial wafer according to claim 1, wherein the atomic layer is formed as a monoatomic layer.
3. Method for manufacturing an epitaxial wafer according to claim 1 or 2, characterised in that SiH is used4And a gas forming a region starting from the atomic layer to at least 5nm in a region adjacent to the atomic layer in a region where the epitaxial layer is formed.
4. The method for manufacturing 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. A method for producing an epitaxial wafer according to any one of claims 1 to 4, characterized in that SiH is used2Cl2Gas or SiHCl3A gas in a region where the epitaxial layer is formed except for the SiH4The region other than the region where the gas is formed.
6. A method for manufacturing an epitaxial wafer according to any one of claims 1 to 5, wherein the epitaxial wafer is a wafer having a wafer thickness,
in the case of forming an oxygen atom layer, forming the atom layer using oxygen gas;
in the case of forming a carbon atom layer, CH is used4A gas forming the atomic layer;
in the case of forming a nitrogen atom layer, NH is used3A gas forming the atomic layer;
in the case of forming a germanium atomic layer, forming the atomic layer using an organometallic gas containing Ge;
in the case of forming a tin atomic layer, forming the atomic layer using an organometallic gas containing Sn;
in the case of forming a boron atomic layer, B is used2H6A gas forming the atomic layer;
in the case of forming a phosphorus atom layer, pH is used3A gas forming the atomic layer.
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