CN108573851B - Self-aligned seed layer and preparation method of self-aligned film - Google Patents

Self-aligned seed layer and preparation method of self-aligned film Download PDF

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CN108573851B
CN108573851B CN201710134405.8A CN201710134405A CN108573851B CN 108573851 B CN108573851 B CN 108573851B CN 201710134405 A CN201710134405 A CN 201710134405A CN 108573851 B CN108573851 B CN 108573851B
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CN108573851A (en
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三重野文健
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Zing Semiconductor Corp
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Abstract

The invention provides a self-aligned seed crystal layer and a preparation method of a self-aligned film, wherein a mask layer made of amorphous carbon is formed on a substrate, the mask layer is patterned to expose part of the substrate, and then a first seed crystal layer and a second seed crystal layer are sequentially formed on the exposed substrate, the dipole moment of the amorphous carbon is smaller, so that the adsorption force ratio of the first seed crystal layer to the amorphous carbon is smaller, the first seed crystal layer on the mask layer is easy to remove, and the efficiency of preparing the self-aligned seed crystal layer is improved; meanwhile, the film is formed on the second seed layer of the self-aligned seed layer, so that the surface flatness of the film can be improved, and an atomically flat surface is achieved, and the self-aligned film with the atomically flat surface is obtained.

Description

Self-aligned seed layer and preparation method of self-aligned film
Technical Field
The invention relates to the field of semiconductor manufacturing, in particular to a self-aligned seed crystal layer and a preparation method of a self-aligned film.
Background
With the continuous reduction of the size of semiconductor devices, the semiconductor manufacturing process has entered the deep submicron era and developed towards ultra-deep submicron, however, with the continuous increase of the density of integrated circuits, higher requirements are also put on the performance and stability of semiconductor devices. The flatness of a thin film, such as a silicon film, formed during the fabrication of a semiconductor device has a significant impact on the performance of the subsequently formed semiconductor device.
In the prior art, a thin film layer with an atomically flat surface is generally obtained by epitaxially growing silicon (Si), silicon germanium (SiGe) or germanium (Ge), however, the method requires a relatively high temperature during the manufacturing process, and for most silicon-on-insulator (SOI), obtaining a flat surface and high crystallinity requires a plurality of process steps, which ultimately results in increased production cost and limited final application.
In addition, three-dimensional integrated digital computer (3DIC) requires an active layer (active layers) to be formed on an insulator, and also requires a flat surface for the active layer, however, it is difficult to obtain an atomically flat surface for a relatively thin active layer on an insulator. The prior art adopts Deposition methods such as ALD (Atomic Layer Deposition), CVD (Chemical Vapor Deposition), and the like, which cannot meet the requirements.
In addition, in the process of manufacturing the self-aligned film, the flatness of the film is affected by the selection, deposition, etching, removal of the film on the mask layer and other processes of the mask layer.
Therefore, how to obtain a self-aligned thin film with an atomically flat surface is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a self-aligned seed crystal layer and a preparation method of a self-aligned film, and the self-aligned seed crystal layer and the self-aligned film with atomically flat surfaces are obtained.
The technical scheme of the invention is a preparation method of a self-aligned seed crystal layer, which comprises the following steps:
providing a substrate, and forming a mask layer on the substrate, wherein the mask layer is made of amorphous carbon;
patterning the mask layer, forming a groove in the mask layer and exposing a part of the substrate;
and sequentially forming a first seed crystal layer and a second seed crystal layer on the exposed substrate.
Further, gas containing disiloxane is introduced to the substrate, and the first seed crystal layer is formed on the substrate; and introducing gas containing cyclopentasilane to the substrate to form a second seed layer on the first seed layer.
Further, in the processes of forming the first seed layer and forming the second seed layer, the gas introduced to the substrate further includes an inert gas.
Further, after forming the first seed layer and before forming the second seed layer, the method further includes: and introducing inert gas to the first seed crystal layer, and removing the first seed crystal layer on the mask layer.
Further, the inert gas is argon.
Further, the first seed layer is a single layer or a double layer; the second seed layer is a single layer, a double layer or a triple layer.
Further, before the mask layer is formed, an insulating layer is formed on the substrate.
Furthermore, the insulating layer is made of silicon oxide or/and silicon nitride.
Correspondingly, the invention also provides a preparation method of the self-aligned film, which comprises the following steps:
providing a self-aligned seed layer prepared by the preparation method of the self-aligned seed layer;
forming a thin film on the self-aligned seed layer.
Further, the film is a silicon film, a germanium film or a silicon germanium film.
Furthermore, a gas containing silicon or/and germanium and hydrogen are introduced into the self-aligned seed crystal layer to form a film on the self-aligned seed crystal layer.
Further, the gas containing silicon is disilane, and the gas containing germanium is germane.
Further, the reaction gas for forming the silicon thin film is disilane and hydrogen, the reaction gas for forming the germanium thin film is germane and hydrogen, and the reaction gas for forming the silicon-germanium thin film is disilane, germane and hydrogen.
Compared with the prior art, the self-aligned seed crystal layer and the preparation method of the self-aligned film provided by the invention have the advantages that the mask layer made of amorphous carbon is formed on the substrate, part of the substrate is exposed by patterning the mask layer, and then the first seed crystal layer and the second seed crystal layer are sequentially formed on the exposed substrate, the dipole moment of the amorphous carbon is smaller, so that the adsorption force ratio of the first seed crystal layer to the amorphous carbon is smaller, the first seed crystal layer on the mask layer is easy to remove, and the efficiency of preparing the self-aligned seed crystal layer is improved; meanwhile, the film is formed on the second seed layer of the self-aligned seed layer, so that the surface flatness of the film can be improved, and an atomically flat surface is achieved, and the self-aligned film with the atomically flat surface is obtained.
Drawings
Fig. 1 is a flowchart illustrating a method for preparing a self-aligned seed layer according to an embodiment of the present invention.
Fig. 2to 6 are schematic structural diagrams of steps of a method for preparing a self-aligned seed layer according to an embodiment of the present invention.
Fig. 7 is a schematic structural diagram of a self-aligned film according to an embodiment of the invention.
Detailed Description
In order to make the contents of the present invention more clearly understood, the contents of the present invention will be further described with reference to the accompanying drawings. The invention is of course not limited to this particular embodiment, and general alternatives known to those skilled in the art are also covered by the scope of the invention.
The present invention is described in detail with reference to the drawings, and for convenience of explanation, the drawings are not enlarged partially according to the general scale, and should not be construed as limiting the present invention.
The core idea of the invention is as follows: forming a mask layer made of amorphous carbon on a substrate, patterning the mask layer to expose part of the substrate, and then sequentially forming a first seed crystal layer and a second seed crystal layer on the exposed substrate, wherein the dipole moment of the amorphous carbon is smaller, so that the adsorption force of the first seed crystal layer and the amorphous carbon is smaller, and the first seed crystal layer on the mask layer is easy to remove, thereby improving the efficiency of preparing the self-aligned seed crystal layer; meanwhile, the film is formed on the second seed layer of the self-aligned seed layer, so that the surface flatness of the film can be improved, and an atomically flat surface is achieved, and the self-aligned film with the atomically flat surface is obtained.
Fig. 1 is a flowchart of a method for preparing a self-aligned seed layer according to an embodiment of the present invention, and as shown in fig. 1, the present invention provides a method for preparing a self-aligned seed layer, including the following steps:
step S01: providing a substrate, and forming a mask layer on the substrate, wherein the mask layer is made of amorphous carbon;
step S02: patterning the mask layer, forming a groove on the mask layer, and exposing a part of the substrate;
step S03: and sequentially forming a first seed crystal layer and a second seed crystal layer on the exposed substrate.
Fig. 2to 6 are schematic structural diagrams of steps of a method for preparing a self-aligned seed layer according to an embodiment of the present invention, and please refer to fig. 1, and refer to fig. 2to 6, to describe in detail the method for preparing a self-aligned seed layer according to the present invention:
in step S01, a substrate 10 is provided, and a mask layer 30 is formed on the substrate 10, wherein the mask layer 30 is made of amorphous carbon, as shown in fig. 2.
In this embodiment, the substrate 10 may be a silicon substrate, a silicon germanium substrate, or a Silicon On Insulator (SOI), or other semiconductor substrates known to those skilled in the art. Preferably, before forming the mask layer 30, an insulating layer 20 is first formed on the substrate 10, where the insulating layer 20 is made of silicon oxide and/or silicon nitride, that is, the insulating layer 20 is a single layer and made of silicon oxide or silicon nitride, or the insulating layer 20 is a double-layer or multi-layer and made of silicon oxide and silicon nitride, for example, a layer of silicon oxide is first formed on the substrate 10 and a layer of silicon nitride is formed on the silicon oxide. The material of the insulating layer 20 may also be other insulating materials known to those skilled in the art.
And then forming a mask layer 30 on the insulating layer 20, wherein the mask layer 30 is made of amorphous carbon. In the present invention, the selection of amorphous carbon as mask layer 30 has some advantages that other materials do not have, such as: the amorphous carbon has better light transmission, and is more beneficial to layer alignment (overlap) in photoetching; the amorphous carbon has higher hardness and higher etching selection ratio compared with other materials; amorphous carbon is a very easy to remove material, etc. In the present embodiment, the amorphous carbon layer is formed by a deposition process, which is one of Low Pressure Chemical Vapor Deposition (LPCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), ultra-high vacuum chemical vapor deposition (UHVCVD), Rapid Thermal Chemical Vapor Deposition (RTCVD), Physical Vapor Deposition (PVD), Atomic Layer Deposition (ALD), and Molecular Beam Epitaxy (MBE), or other methods known to those skilled in the art.
In step S02, the mask layer 30 is patterned, and a recess 31 is formed in the mask layer 30 to expose a portion of the insulating layer 20, thereby forming the structure shown in fig. 3.
The step of patterning the mask layer 30 may include: a layer of photoresist (not shown) is spin-coated on the surface of the mask layer 30, the photoresist is thin, and after selective exposure and development, the patterned mask layer 30 is formed. Further, to eliminate the interference of the reflected light in the exposure process, the method may further include: depositing an anti-reflective dielectric layer (DARC) (not shown) on the surface of the mask layer 30, forming a photoresist on the anti-reflective dielectric layer, etching the anti-reflective dielectric layer and the mask layer 30 by using the patterned photoresist as a mask after exposure and development, and removing the photoresist residue and the anti-reflective dielectric layer. Finally, a groove 31 is formed in the mask layer 30, and the groove 31 exposes a portion of the insulating layer 20.
In step S03, a first seed layer 40 and a second seed layer 50 are sequentially formed on the exposed insulating layer 20, so as to form the structure shown in fig. 6.
First, a gas containing disiloxane is introduced into the substrate 10 to form a first seed layer 40 on the surface of the mask layer 30 and the exposed surface of the insulating layer 20, as shown in fig. 4.
The substrate 10 with the patterned mask layer 30 formed thereon was placed in a reaction chamber into which disiloxane ((H) was introduced3Si)2O) forming a first seed layer (H) on the surface of the mask layer 30 and the exposed insulating layer 203Si)2And an O layer 30. In this embodiment, the gas introduced into the reaction chamber further includes an inert gas. Preferably, in this embodiment, the inert gas is argon (Ar).
The disiloxane ((H)3Si)2O) is an organosilicon compound with a silicon-oxygen-silicon group, has a comparatively low Melting Point and Boiling Point, and has a Melting Point (m.p.) of-144 ℃ and a Boiling Point (bonding Point, b.p.) of-15.2 ℃. In this embodiment, the disiloxane is in a gaseous state, and the disiloxane is directly introduced into the reaction chamber through the gas channel.
The temperature of the reaction chamber is 100-300 ℃, the pressure in the reaction chamber is 0.1-3.0 Torr, and the gas flow rate, wherein the flow rate of disiloxane is 50-500 sccm, and the flow rate of inert gas is 100-1000 sccm. Preferably, in this embodiment, the process conditions for forming the first seed layer 40 are as follows: the temperature of the reaction chamber is 200 ℃, the pressure in the chamber is 0.2Torr, and the gas flow: the reaction time for forming the first seed layer 40 is 2min, with 200sccm of disiloxane and 1000sccm of argon gas. Finally, the first seed layer 40 is formed by adsorbing oxygen in the disiloxane on the surface of the mask layer 30 or the surface of the insulating layer 20.
The first seed layer 40 is a single layer or a double layer, i.e. a single layer of the first seed layer 40 may be formed, or a double layer of the first seed layer 40 may be formed, i.e. the reaction is terminated after a layer of the first seed layer 40 is formed, and then a layer of the first seed layer 40 is formed on the first seed layer 40. The process conditions for forming the bilayer of the first seed layer 40 may be the same, partially the same, or different. When the process conditions for forming the double layer of the first seed layer 40 are completely the same, it can also be considered that the first seed layer 40 is formed continuously with twice the thickness, during which there is no pause in the reaction. It is understood that the present embodiment provides a preferred number of layers, and in other embodiments, the first seed layer 40 may be larger than two layers.
Then, an inert gas is continuously introduced onto the first seed layer 40, and the first seed layer 40 on the mask layer 30 is removed, thereby forming the structure shown in fig. 5. Specifically, the substrate 10 after the first seed layer 40 is formed is placed in a reaction chamber, an inert gas is continuously introduced from the top end of the reaction chamber (relative to the substrate 10, the reaction chamber opening above the substrate 10), and then an exhaust gas is continuously discharged from the bottom end of the reaction chamber. Because the dipole moment of the amorphous carbon is smaller, the adsorption force between the first seed crystal layer 40 and the mask layer 30 is smaller, and the first seed crystal layer 40 on the mask layer 30 can be removed through the gas flow of the inert gas, so that the first seed crystal layer 40 is prevented from being removed by an etching method, the process time is saved, the process difficulty is reduced, and the mask layer 30 is prevented from being damaged by etching.
At this time, the temperature of the reaction chamber is 50-150 ℃, the pressure in the chamber is 0.05-0.15 Torr, and the flow rate of the inert gas is 1000-3000 sccm. Preferably, in this embodiment, the temperature of the reaction chamber is 100 ℃, the pressure in the chamber is 0.1Torr, and the flow rate of the inert gas is 2000sccm until the first seed layer 40 on the mask layer 30 is removed, so that only the exposed insulating layer 20 remains with the first seed layer 40. In this embodiment, the inert gas is preferably argon.
Finally, a gas containing cyclopentasilane is introduced into the substrate 10 to form a second seed layer 50 on the first seed layer 40, as shown in fig. 6.
In this embodiment, the gas introduced into the substrate 10 further includes an inert gas. The Cyclopentasilane (CPS) is a five-membered ring compound surrounded by silane, is a liquid silicide similar to a benzene ring, needs to be mixed with an inert gas, is introduced into a reaction chamber in which the substrate 10 is placed under the action of a part of the inert gas, and is further added with the inert gas in order to improve the uniformity of the mixed gas. In this embodiment, the inert gas is preferably argon.
Introducing a mixed gas of cyclopentasilane and an inert gas into the reaction chamber to form a second seed layer SiH on the first seed layer 40250. The temperature of the reaction chamber is 100-500 ℃, the pressure in the reaction chamber is 0.1-3.0 Torr, and the gas flow is as follows: wherein the flow rate of the mixed gas of the cyclopentasilane and the inert gas is 50sccm to 500sccm, and the flow rate of the inert gas is 100sccm to 1000 sccm. Preferably, in this embodiment, the process conditions for forming the second seed layer 50 are as follows: the temperature of the reaction chamber is 300 ℃, the pressure in the chamber is 0.2Torr, and the gas flow rate is as follows: wherein the flow rate of the mixed gas of the cyclopentasilane and the inert gas is 200sccm, and the flow rate of the inert gas is 1000 sccm. The silylene produced by the thermal decomposition of the cyclopentasilaneAlkyl groups (SiH2) are adsorbed onto the first seed layer 40 forming the second seed layer 50. The reaction time for forming the second seed layer 40 was 2 min.
The second seed layer 50 may be a single layer, a double layer, or a triple layer, that is, a single layer of the second seed layer 50 may be formed, or a double layer or a triple layer of the second seed layer 50 may be formed, and it is understood that the formation of the double layer or the triple layer of the second seed layer 50 is completed by introducing cyclopentasilane and an inert gas into a reaction chamber, stopping the introduction of the gas after the second seed layer 50 having a predetermined thickness is formed on the first seed layer 40, and ending the film formation, at this time, the gas in the reaction chamber may be discharged by the introduction of the inert gas, and then introducing the cyclopentasilane and the inert gas again to complete the film formation of the second seed layer 50, and so on, the film formation of the third layer of the second seed layer 50 is completed. The process conditions for forming the double or triple layers of the second seed layer 50 may be identical, partially identical, or different. When the process conditions for forming the double or triple layer of the second seed layer 50 are completely the same, it can also be considered that the second seed layer 50 is continuously formed with a double thickness or a triple thickness, during which there is no stop of the reaction. It should be noted that, in this embodiment, a preferred number of layers is given, and in other embodiments, the second seed layer 50 may be larger than three layers.
Preferably, the method further includes removing the second seed layer 50 on the mask layer 30, and leaving the second seed layer 50 on the first seed layer 40. A photoresist layer may be coated on the second seed layer 50, the second seed layer 50 on the mask layer 30 is exposed by exposure and development, then the second seed layer 50 is removed by etching, and finally the photoresist layer is removed, forming a self-aligned seed layer as shown in fig. 6.
In the preparation method of the self-aligned seed crystal layer, the mask layer 30 made of the amorphous carbon is adopted, the dipole moment of the amorphous carbon is smaller, so that the adsorption force of the first seed crystal layer 40 and the amorphous carbon is smaller, the first seed crystal layer 40 on the mask layer 30 can be removed by introducing the inert gas, the first seed crystal layer 40 is prevented from being removed by an etching method, the process time is saved, the process difficulty is reduced, the mask layer 30 is prevented from being possibly damaged by etching, and the efficiency of preparing the self-aligned seed crystal layer is improved.
Correspondingly, the invention also provides a preparation method of the self-aligned thin film, which provides a self-aligned seed crystal layer prepared by the preparation method of the self-aligned seed crystal layer, and forms the thin film on the self-aligned seed crystal layer to form the structure shown in fig. 7.
Specifically, a thin film 60 is formed on the second seed layer 50 by introducing a reaction gas into the reaction chamber. The film is a silicon film, a germanium film or a silicon germanium film. The reaction gas comprises a silicon-containing or/and germanium-containing gas and hydrogen (H)2). The process conditions for forming the thin film 60 are as follows: the temperature of the reaction chamber is 100-500 ℃, the pressure in the reaction chamber is 0.1-3.0 Torr, and the gas flow is as follows: wherein the flow rate of the silicon-containing gas is 50sccm to 500sccm or/and the flow rate of the germanium-containing gas is 50sccm to 500sccm, and the flow rate of the hydrogen gas is 100sccm to 1000 sccm. Preferably, in this embodiment, the process conditions for forming the thin film 60 on the second seed layer 50 are as follows: the temperature of the reaction chamber is 300 ℃, the pressure in the chamber is 0.2Torr, and the gas flow rate is as follows: wherein the flow rate of the silicon-containing gas is 200sccm or/and the flow rate of the germanium-containing gas is 200sccm, the flow rate of the hydrogen gas is 1000sccm, the reaction time for forming the thin film 60 is 5min, and the thin film 60 with the thickness of about 10nm is finally formed.
Preferably, the silicon-containing gas is disilane (Si)2H6) The germanium-containing gas is germane (GeH)4). Specifically, disilane and hydrogen are introduced into the reaction chamber, and a silicon thin film is formed on the second seed layer 50; introducing germane and hydrogen into the reaction chamber to form a germanium film on the second seed layer 50; introducing disilane, germane and hydrogen into the reaction chamber, and forming a silicon germanium film on the second seed layer 50.
Preferably, the method further comprises removing the film 60 on the mask layer 30, and leaving the film 60 on the second seed layer 50 to form a self-aligned film as shown in fig. 7.
In summary, according to the self-aligned seed layer and the method for preparing a self-aligned thin film provided by the present invention, the mask layer made of amorphous carbon is formed on the substrate, the mask layer is patterned to expose a portion of the substrate, and then the first seed layer and the second seed layer are sequentially formed on the exposed substrate, the dipole moment of the amorphous carbon is small, so that the adsorption force between the first seed layer and the amorphous carbon is small, and the first seed layer on the mask layer is easily removed, thereby improving the efficiency of preparing the self-aligned seed layer; meanwhile, the film is formed on the second seed layer of the self-aligned seed layer, so that the surface flatness of the film can be improved, and an atomically flat surface is achieved, and the self-aligned film with the atomically flat surface is obtained.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.

Claims (11)

1. A method for preparing a self-aligned seed layer, comprising the steps of:
providing a substrate, and forming a mask layer on the substrate, wherein the mask layer is made of amorphous carbon;
patterning the mask layer, forming a groove in the mask layer and exposing a part of the substrate;
forming a first seed layer on the exposed substrate, the first seed layer being (H)3Si)2An O layer;
introducing inert gas to the first seed crystal layer, and removing the first seed crystal layer on the mask layer;
forming a second seed layer on the exposed substrate;
and forming a silicon film, a germanium film or a silicon germanium film on the second seed layer.
2. The method of claim 1, wherein the first seed layer is formed on the substrate by introducing a gas comprising disiloxane onto the substrate; and introducing gas containing cyclopentasilane to the substrate to form a second seed layer on the first seed layer.
3. The method for preparing a self-aligned seed layer of claim 2, wherein the gas introduced into the substrate during the formation of the first seed layer and the formation of the second seed layer further comprises an inert gas.
4. The method for preparing a self-aligned seed layer of claim 3 wherein the inert gas is argon.
5. The method of preparing a self-aligned seed layer according to any of claims 1to 4, wherein the first seed layer is a single layer or a bilayer; the second seed layer is a single layer, a double layer or a triple layer.
6. The method for preparing a self-aligned seed layer of claim 5, wherein an insulating layer is formed on the substrate prior to forming the mask layer.
7. The method for preparing a self-aligned seed layer according to claim 6, wherein the insulating layer is made of silicon oxide or/and silicon nitride.
8. A method for preparing a self-aligned film, comprising the steps of:
providing a self-aligned seed layer prepared by the method for preparing the self-aligned seed layer according to any one of claims 1to 7;
forming a silicon film, a germanium film or a silicon germanium film on the self-aligned seed layer.
9. The method of claim 8, wherein a gas comprising Si or/and Ge and hydrogen are flowed over the self-aligned seed layer to form a film on the self-aligned seed layer.
10. The method of claim 9, wherein the silicon-containing gas is disilane and the germanium-containing gas is germane.
11. The method of claim 10, wherein the reaction gas for forming the silicon thin film is disilane and hydrogen, the reaction gas for forming the germanium thin film is germane and hydrogen, and the reaction gas for forming the silicon germanium thin film is disilane, germane and hydrogen.
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