CN110896022B - Method for forming oxide layer in semiconductor structure - Google Patents
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- CN110896022B CN110896022B CN201811069648.9A CN201811069648A CN110896022B CN 110896022 B CN110896022 B CN 110896022B CN 201811069648 A CN201811069648 A CN 201811069648A CN 110896022 B CN110896022 B CN 110896022B
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- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
- H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
- H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
- H01L21/02238—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
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Abstract
The invention provides a method for forming an oxide layer in a semiconductor structure, which comprises the following steps: providing a semiconductor substrate; performing a first oxidation process to form a first oxidation layer on the semiconductor substrate under a first pressure; and under a second pressure, executing a second oxidation process to form a second oxidation layer on the first oxidation layer, and obtaining the oxidation layer; wherein the oxide layer is composed of the first oxide layer and the second oxide layer, the first pressure is higher than the second pressure, and a reaction rate for forming the first oxide layer is less than a reaction rate for forming the second oxide layer. By adopting the two-step oxidation method, the uniformity of the thickness of the oxide layer can be improved, and the yield of products can be improved. The method has simple process and low cost, and is suitable for the growth of oxide layers of semiconductor structures, such as gate oxide layers, STI oxide layers, sacrificial oxide layers, sidewall oxide layers, liner oxide layers, and the like, including but not limited to the above oxide layers.
Description
Technical Field
The invention relates to the field of semiconductor manufacturing, in particular to a method for forming an oxide layer in a semiconductor structure.
Background
In the semiconductor manufacturing process, an oxide layer, such as a capacitor gate oxide layer, is currently grown by in-situ steam oxidation (ISSG). The thickness of the oxide film grown by the traditional ISSG method can change along with different positions on a silicon wafer, so that the uniformity of the film is influenced, the thickness of the gate oxide layer on different chips on one wafer is different, and the chip performance is poor or even fails due to over-thickness or over-thinness, so that the yield is reduced.
Therefore, a new method for forming an oxide layer of a semiconductor structure is needed to solve the above-mentioned problems in the prior art.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The present invention provides a method for forming an oxide layer in a semiconductor structure, so as to solve the problem of the conventional in-situ steam oxidation (ISSG) method that the thickness of the oxide layer is not uniform, thereby reducing the yield of the product.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for forming an oxide layer in a semiconductor structure, which comprises the following steps:
providing a semiconductor substrate;
performing a first oxidation process to form a first oxidation layer on the semiconductor substrate under a first pressure; and
executing a second oxidation process to form a second oxide layer on the first oxide layer under a second pressure, and obtaining the oxide layer;
wherein the oxide layer is composed of the first oxide layer and the second oxide layer, the first pressure is higher than the second pressure, and a reaction rate for forming the first oxide layer is less than a reaction rate for forming the second oxide layer.
According to one embodiment of the invention, the first oxidation process and the second oxidation process both employ an in situ steam oxidation process.
According to an embodiment of the present invention, the first pressure is 7to 15torr, and the second pressure is 1 to 7 torr.
According to one embodiment of the present invention, the reaction rate of forming the first oxide layer is 0.01nm/s to 0.25nm/s, and the reaction rate of forming the second oxide layer is 0.25nm/s to 0.8 nm/s.
According to one embodiment of the invention, the first oxide layer and the second oxide layer each have an undulating surface, the oxide layers having a flat surface.
According to one embodiment of the present invention, the thickness of the oxide layer is 2nm to 30 nm. According to one embodiment of the present invention, the thickness of the first oxide layer is 15% to 40% of the thickness of the oxide layer, the thickness of the second oxide layer is 85% to 60% of the thickness of the oxide layer, and the thickness of the first oxide layer and the thickness of the second oxide layer are both average thicknesses.
According to an embodiment of the present invention, the reaction time for forming the first oxide layer is 1 to 60 seconds, and the reaction time for forming the second oxide layer is 1 to 60 seconds.
According to one embodiment of the invention, the first oxidation process and the second oxidation process are both carried out in an environment of a first gas selected from one or more of oxygen, ozone, nitrous oxide, nitrogen dioxide and nitric oxide and a second gas selected from one or more of hydrogen and ammonia.
According to one embodiment of the present invention, the first oxidation process and the second oxidation process are performed at the same concentration of the second gas, and the concentration of the second gas is 0.5% to 35%.
According to one embodiment of the present invention, the reaction temperature of the first oxidation process and the second oxidation process is the same, and the reaction temperature ranges from 800 to 1200 ℃.
According to one embodiment of the present invention, the oxide layer is selected from one or more of a gate oxide layer, a shallow trench isolation structure oxide layer, a sacrificial oxide layer, a sidewall oxide layer, and a liner oxide layer.
According to one embodiment of the present invention, the material of the semiconductor substrate is selected from one or more of silicon and silicon nitride.
According to the technical scheme, the invention has the beneficial effects that:
the invention controls the reaction pressure and the reaction rate by adopting a two-step ISSG method, effectively avoids the characteristic of uneven oxide layer thickness growth grown by the traditional ISSG method, thereby controlling the consistency of the wafer, reducing the possibility of chip failure and further improving the product yield. The method has simple process and low cost, and is suitable for the growth of oxide layers of various semiconductor structures, such as a gate oxide layer, a Shallow Trench Isolation (STI) oxide layer, a sacrificial oxide layer, a side wall oxide layer, a liner oxide layer and the like.
Drawings
In order that the embodiments of the invention may be more readily understood, reference should now be made to the following detailed description taken in conjunction with the accompanying drawings. It should be noted that, in accordance with industry standard practice, various components are not necessarily drawn to scale and are provided for illustrative purposes only. In fact, the dimensions of the various elements may be arbitrarily expanded or reduced for clarity of discussion.
FIG. 1 illustrates a schematic cross-sectional view of a semiconductor substrate of the prior art;
FIG. 2 shows the film thickness profile of a silicon dioxide film at different pressures over a wafer;
FIGS. 3 and 4 are schematic views showing partial cross-sectional shapes of silicon dioxide films grown by a conventional ISSG oxidation process;
FIG. 5 is a process flow diagram illustrating a method for forming an oxide layer according to an embodiment of the invention;
FIG. 6 is a schematic diagram illustrating a partial cross-sectional structure of an oxide layer formed in accordance with one embodiment of the present invention;
FIGS. 7 and 8 show the thickness of the silicon dioxide films grown at different positions on the wafers in comparative example and example 1, respectively;
FIG. 9 shows the film thickness profiles of the silica thin films on the wafers in comparative example and example 1.
Wherein the reference numerals are as follows:
100, 200: semiconductor substrate
101: groove
102: silicon dioxide film
202: oxide layer
202 a: first oxide layer
202 b: second oxide layer
a1, a2, a3, b1, b2, b 3: thickness of silicon dioxide film
Detailed Description
The following provides many different embodiments, or examples, for implementing different features of embodiments of the invention. Specific examples of components and arrangements are described below to simplify the present embodiments. These are, of course, merely examples and are not intended to limit embodiments of the invention. Embodiments of the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Forming a component on, connected to, and/or coupled to another component in embodiments of the invention may include forming embodiments in which the component directly contacts the other component, and may also include forming additional components between the components such that the components do not directly contact. Furthermore, spatially relative terms, such as "lower," "upper," "horizontal," "vertical," "above …," "above," "below …," "below …," "upward," "downward," "top," "bottom," and the like, may be used herein to facilitate describing the relationship of one element to another element of an embodiment of the invention (e.g., "horizontally," "vertically," "upwardly," "downwardly," etc.). These spatially relative terms are intended to encompass different orientations of the device in which the components are incorporated.
The present invention will be explained in further detail by taking the formation process of the gate oxide layer as an example.
Fig. 1 is a cross-sectional view of a semiconductor substrate in the prior art, as shown in fig. 1, the semiconductor substrate 100 has a plurality of trenches 101, and a conventional ISSG oxidation process is performed on the trenches 101, for example, a silicon (Si) substrate, so as to form an oxide layer, i.e., silicon dioxide (SiO) on the sidewalls of the trenches 1012) A membrane 102. Wherein the conventional ISSG oxidation process is carried out in hydrogen (H)2) With oxygen (O)2) The ISSG oxidation process is performed at a temperature of 800-1200 ℃ and a pressure of 1-15 Torr, and the ISSG oxidation process is performed in an oxygen-rich atmosphere, that is, the amount of oxygen is set to be higher than that of hydrogen. Preferably, the hydrogen content is 0.5-35%. The oxidation rate is controlled by the O and OH radicals produced by the reaction of hydrogen and oxygen. The reaction equation can be expressed as follows:
H2+O2→H2O+O+OH
however, under the same process conditions, when the reaction pressure is maintained constant, the gate oxide layer is grown by the conventional ISSG oxidation process, so that the thickness of the silicon dioxide varies with the position on the wafer, and fig. 2 shows the film thickness distribution curve of the silicon dioxide film on the wafer under different pressures, wherein the abscissa is the radial dimension of the wafer in mm (0 point is the center of the wafer) and the ordinate is the film thickness of the silicon dioxide. As can be seen from fig. 2, the growth thickness of the silicon dioxide film on the wafer surface is different under different pressures, which further affects the uniformity of the oxide layer. Fig. 3 and 4 are schematic views showing partial cross-sectional shapes of silicon dioxide films grown by a conventional ISSG oxidation process, in which fig. 3 is a silicon dioxide film grown under a higher pressure condition, and fig. 4 is a silicon dioxide film grown under a lower pressure condition. It can be seen that the conventional ISSG oxidation process does not produce a uniform oxide layer.
To this end, the present invention provides a method for forming an oxide layer in a semiconductor structure, and fig. 5 shows a process flow diagram of the method for forming an oxide layer according to an embodiment of the present invention, which includes:
providing a semiconductor substrate;
performing a first oxidation process to form a first oxidation layer on the semiconductor substrate under a first pressure; and
executing a second oxidation process to form a second oxide layer on the first oxide layer under a second pressure, and obtaining the oxide layer;
wherein the oxide layer is composed of the first oxide layer and the second oxide layer, the first pressure is higher than the second pressure, and a reaction rate for forming the first oxide layer is less than a reaction rate for forming the second oxide layer.
In some implementations, the first oxidation process and the second oxidation process both employ an in-situ steam oxidation (ISSG) process. ISSG is a novel low-pressure rapid thermal oxidation annealing process technology, in which diluted water vapor is formed on the surface of a wafer by using high-purity oxygen and hydrogen in a low-pressure rapid thermal oxidation chamber, and a chemical reaction similar to combustion occurs on the surface of the wafer when the wafer is rapidly oxidized at a high temperature. The reaction generates a plurality of gas-phase active free radicals in the cavity, most of the free radicals are atomic oxygen which can easily react with silicon atoms, the atomic oxygen has strong oxidation effect and can form a film with good uniformity with the silicon atoms, the formed film has relatively few internal defects, the silicon-oxygen interface is smooth, and the quality of the formed film is much higher compared with that of silicon dioxide grown by using a furnace tube.
The invention discovers that through the two-step oxidation process, a thin oxide layer grows at a relatively high pressure and a relatively low reaction rate, the pressure is adjusted to a relatively low range under the condition that other process conditions are not changed, and the oxide layer grows at a relatively high reaction rate until the required thickness is achieved. Fig. 6 shows a schematic partial cross-sectional structure of an oxide layer formed according to an embodiment of the present invention, which includes a first oxide layer 202a and a second oxide layer 202b on a semiconductor substrate 200, which together form a final oxide layer 202. As can be seen from fig. 6, the oxide layer with uniform thickness and good uniformity is finally obtained through the two-step oxidation process. Therefore, the method can effectively avoid the characteristic that the thickness of the grid oxide layer grows non-uniformly on the silicon wafer, thereby controlling the consistency of the thickness of the grid oxide layer of each chip on one wafer, achieving better characteristics, reducing the possibility of chip failure and improving the yield of products.
In some embodiments, the first pressure is 7to 15torr and the second pressure is 1 to 7 torr.
In some embodiments, the reaction rate for forming the first oxide layer is 0.01nm/s to 0.25nm/s, and the reaction rate for forming the second oxide layer is 0.25nm/s to 0.8 nm/s.
In some embodiments, the thickness of the oxide layer is defined as a base thickness, the thickness of the first oxide layer is 15% to 40% of the base thickness, and the thickness of the second oxide layer is 85% to 60% of the base thickness. Wherein the base thickness is 2nm to 30 nm. The first oxide layer and the second oxide layer both have undulating surfaces which are fitted to each other, so that the formed oxide layer has a flat surface, and the thickness of the first oxide layer and the thickness of the second oxide layer are both average thicknesses.
In some embodiments, the reaction time for forming the first oxide layer is 1-60 s, and the reaction time for forming the second oxide layer is 1-60 s.
In some embodiments, the first oxidation process and the second oxidation process are both performed in the environment of a first gas and a second gas, the first gas including, but not limited to, oxygen, ozone, nitrous oxide, nitrogen dioxide, nitric oxide, or a combination thereof, preferably oxygen. The second gas includes, but is not limited to, hydrogen, ammonia, or a combination thereof, preferably hydrogen.
In some embodiments, the first oxidation process and the second oxidation process are performed at the same concentration of the second gas, and the concentration of the second gas is 0.5% to 35%.
In some embodiments, the reaction temperature of the first oxidation process and the second oxidation process is the same, and the reaction temperature ranges from 800 ℃ to 1200 ℃.
In some embodiments, the oxide layer is one or more of a gate oxide layer, an oxide layer in a shallow trench isolation structure, or a sacrificial oxide layer, or a sidewall oxide layer, or a liner oxide layer, but the method of the present invention is not limited to the above-mentioned oxide layer, and any structure that can obtain an oxide layer with a uniform thickness by using the method can be applied to the present invention.
In some embodiments, the material of the semiconductor substrate includes, but is not limited to, silicon nitride, and the like, and the oxide layer formed includes, but is not limited to, silicon dioxide.
The invention is further illustrated by the following specific examples:
example 1
Providing a silicon substrate with a plurality of grooves, and carrying out ISSG oxidation process on the silicon substrate under the pressure of 7.5torr to form a first layer of silicon dioxide film in the grooves of the silicon substrate. The ISSG oxidation process adopts a gas environment of hydrogen and oxygen, wherein the concentration of the hydrogen is 3 percent, the concentration of the oxygen is 97 percent, the reaction temperature is 800 ℃, the reaction rate is 0.1nm/s, and the reaction time is 15 s.
And then, keeping the process conditions unchanged, adjusting the pressure to 6torr, and continuing to perform the ISSG oxidation process of the second step, wherein the reaction rate is 0.3nm/s, and the reaction time is 12s, so that a second silicon dioxide film is obtained, namely the growth of a silicon dioxide oxidation layer is completed.
Comparative example
The same silicon substrate as in example 1 was subjected to an ISSG oxidation process at a pressure of 7.5torr to form a silicon dioxide film. The ISSG oxidation process adopts a gas environment of hydrogen and oxygen, wherein the concentration of the hydrogen is 3 percent, the concentration of the oxygen is 97 percent, the reaction temperature is 800 ℃, the reaction rate is 0.1nm/s, and the reaction time is 50 s.
Test example
The silica membranes obtained in example 1 and comparative example were tested. FIGS. 7 and 8 show the thicknesses of the silicon dioxide films grown at different positions of the wafers obtained in comparative example and example 1, respectively, wherein a1, a2 and a3 represent the thicknesses of the silicon dioxide films grown at different positions of the wafers in comparative example, and it can be seen that the thicknesses of a1, a2 and a3 are significantly different; b1, b2, and b3 represent the thicknesses of the silicon dioxide films grown at different positions on the wafer in example 1, and it can be seen that the thicknesses of b1, b2, and b3 are almost the same. Therefore, the oxide layer prepared by the method has small difference of film thickness grown at different positions of the wafer. Further, as shown in fig. 9, the film thickness distribution curves of the silica thin films on the wafer in the comparative example and the example 1 are shown, respectively, and it can be seen from fig. 9 that the range of variation (range) of the silica film thickness obtained in the example 1 is less than 0.5, while the difference of the film thickness of the silica film obtained in the comparative example is significantly large, and the range is less than 2. Wherein, the range value is obtained by measuring the film thickness of different positions of the wafer by an ellipsometer and calculating the difference value.
Therefore, the silicon dioxide film with uniform thickness and good uniformity can be obtained by adopting the two-step oxidation method.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A method for forming an oxide layer in a semiconductor structure comprises the following steps:
providing a semiconductor substrate;
performing a first oxidation process to form a first oxidation layer on the semiconductor substrate under a first pressure; and
executing a second oxidation process to form a second oxide layer on the first oxide layer under a second pressure, and obtaining the oxide layer;
wherein the oxide layer is composed of the first oxide layer and the second oxide layer, the first pressure is higher than the second pressure, and the reaction rate for forming the first oxide layer is lower than the reaction rate for forming the second oxide layer;
the first oxidation process and the second oxidation process are both carried out in an environment of a first gas selected from one or more of oxygen, ozone, nitrous oxide, nitrogen dioxide and nitric oxide and a second gas selected from one or more of hydrogen and ammonia;
the concentration of a second gas for performing the first oxidation process and the second oxidation process is the same, and the concentration of the second gas is 0.5-35%; the reaction temperature of the first oxidation process is the same as that of the second oxidation process, and the range of the reaction temperature is 800-1200 ℃.
2. The method of forming as claimed in claim 1, wherein the first oxidation process and the second oxidation process both employ an in-situ steam oxidation process.
3. The method of claim 1, wherein the first pressure is 7to 15torr and the second pressure is 1 to 7 torr.
4. The method according to claim 1, wherein a reaction rate of the first oxide layer formation is 0.01nm/s to 0.25nm/s, and a reaction rate of the second oxide layer formation is 0.25nm/s to 0.8 nm/s.
5. The method of forming as claimed in claim 1, wherein the first and second oxide layers each have an undulating surface, the oxide layers having a planar surface.
6. The method of claim 5, wherein the oxide layer has a thickness of 2nm to 30 nm.
7. The forming method according to claim 1 or 6, wherein a thickness of the first oxide layer is 15% to 40% of a thickness of the oxide layer, a thickness of the second oxide layer is 85% to 60% of the thickness of the oxide layer, and the thickness of the first oxide layer and the thickness of the second oxide layer are both an average thickness.
8. The method according to claim 1, wherein a reaction time for forming the first oxide layer is 1 to 60 seconds, and a reaction time for forming the second oxide layer is 1 to 60 seconds.
9. The method of claim 1, wherein the oxide layer is selected from one or more of a gate oxide layer, a shallow trench isolation structure oxide layer, a sacrificial oxide layer, a sidewall oxide layer, and a liner oxide layer.
10. The method of claim 1, wherein the semiconductor substrate is made of one or more materials selected from silicon and silicon nitride.
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