CN118086874A - Coating process for plasma enhanced atomic layer deposition - Google Patents
Coating process for plasma enhanced atomic layer deposition Download PDFInfo
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- CN118086874A CN118086874A CN202410509681.8A CN202410509681A CN118086874A CN 118086874 A CN118086874 A CN 118086874A CN 202410509681 A CN202410509681 A CN 202410509681A CN 118086874 A CN118086874 A CN 118086874A
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- 238000000576 coating method Methods 0.000 title claims abstract description 94
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 120
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 354
- 229910052786 argon Inorganic materials 0.000 claims description 177
- 239000007789 gas Substances 0.000 claims description 155
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 128
- 238000010926 purge Methods 0.000 claims description 120
- 239000001307 helium Substances 0.000 claims description 83
- 229910052734 helium Inorganic materials 0.000 claims description 83
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 83
- 239000011248 coating agent Substances 0.000 claims description 74
- 229910052757 nitrogen Inorganic materials 0.000 claims description 63
- 238000007664 blowing Methods 0.000 claims description 59
- 239000002243 precursor Substances 0.000 claims description 31
- 238000007747 plating Methods 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000010408 sweeping Methods 0.000 claims description 3
- 239000007888 film coating Substances 0.000 abstract description 53
- 238000009501 film coating Methods 0.000 abstract description 53
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 description 63
- 238000005086 pumping Methods 0.000 description 45
- 238000010438 heat treatment Methods 0.000 description 32
- 206010037544 Purging Diseases 0.000 description 26
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002352 surface water Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 239000012530 fluid Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
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- 230000008021 deposition Effects 0.000 description 4
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- 230000004888 barrier function Effects 0.000 description 3
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- 230000002349 favourable effect Effects 0.000 description 3
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- 239000012159 carrier gas Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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Abstract
The application discloses a coating process for plasma enhanced atomic layer deposition, which comprises the following steps: placing a workpiece to be plated in a process cavity, wherein the process cavity is provided with a top side and a bottom side which are opposite, the workpiece to be plated is provided with a region to be plated facing the top side, and a middle region is arranged between the region to be plated and the top side; introducing an air flow into the process chamber, the air flow comprising a first air flow and a second air flow, the first air flow being blown out from the top side and toward the zone to be plated, the second air flow being blown out from the middle region and from the periphery of the zone to be plated toward the zone to be plated. According to the film coating process disclosed by the application, each air flow is blown out from different output positions and directions, so that the blockage of the output positions and the risks of introducing impurities into the film layer can be reduced, and the quality of the film layer can be improved.
Description
Technical Field
The application relates to the technical field of plasma enhanced atomic layer deposition, in particular to a coating process of plasma enhanced atomic layer deposition.
Background
Plasma enhanced Atomic Layer Deposition (ALD) is a coating method of plasma assisted Atomic Layer Deposition (ALD), in which plasma energy is mainly used to generate reactive species such as electrons, ions, photons, radicals and excited species, which in turn cause chemical reactions. It has good film composition control and efficient film growth rate compared to conventional ALD.
The quality of the film layer is related to uniformity of the film layer, composition components and the like. In order to improve the quality of a film layer, CN113981412a discloses a film deposition process and a film deposition apparatus, in which carrier gas, reactive gas and source gas are supplied into a process chamber through a gas supply device and a plurality of pipelines arranged at the top side of the process chamber, and each gas is output in a shower manner.
Disclosure of Invention
In view of the prior art, the application provides a coating process for plasma enhanced atomic layer deposition to improve the quality of a film.
The application provides a coating process for plasma enhanced atomic layer deposition, which comprises the following steps:
Placing a workpiece to be plated in a process cavity, wherein the process cavity is provided with a top side and a bottom side which are opposite, the workpiece to be plated is provided with a region to be plated facing the top side, and a middle region is arranged between the region to be plated and the top side;
Introducing an air flow into the process chamber, the air flow comprising a first air flow and a second air flow, the first air flow being blown out from the top side and toward the zone to be plated, the second air flow being blown out from the middle region and from the periphery of the zone to be plated toward the zone to be plated.
Optionally, the first gas flow is divided into a plurality of strands, and the output positions of the strands in the process cavity correspond to the to-be-plated area.
Optionally, the first air flow blows vertically downwards towards the area to be plated.
Optionally, the second air flow is divided into a plurality of streams, and output positions of the streams in the process cavity are distributed at intervals in the circumferential direction of the to-be-plated area.
Alternatively, each second air stream is blown downward and is offset toward the center of the area to be plated.
Optionally, each second air flow is located at the periphery of the area to be plated at the vertical projection position of the output position in the process chamber.
Optionally, the output positions of the second airflows in the process chamber are arranged in a circular ring.
Optionally, the height of each gas flow relative to the output position of the plating zone within the process chamber is adjustable.
Optionally, the coating process further includes: air is pumped from the bottom side of the process chamber.
Optionally, the first airflow includes a first purge airflow and a first coating airflow which are respectively output in different stages;
the second air flow comprises a second sweeping air flow and a second coating air flow which are respectively output in different stages.
Optionally, the process includes a purge stage and first and second plating stages respectively performed before and after the purge stage, wherein:
during the purge phase, the first purge gas stream is blown out simultaneously with the second purge gas stream;
And blowing one of the first coating air flow and the second coating air flow in the first coating stage, and blowing the other of the first coating air flow and the second coating air flow in the second coating stage.
Optionally, the first purge gas stream is helium and/or nitrogen, and the second purge gas stream is argon;
the first coating gas stream includes an oxygen precursor and the second coating gas stream includes an aluminum precursor.
Compared with the prior art, the film coating process provided by the application blows out all air flows from different output positions and different directions, and can reduce the risks of output blockage and impurity introduction into the film layer, thereby being beneficial to improving the quality of the film layer.
Drawings
FIG. 1 is a schematic diagram of a deposition system for plasma enhanced atomic layer deposition according to an embodiment of the present application;
FIG. 2 is a partial schematic view of the output positions of the first and second streams in the process chamber at the vertical projection positions;
FIG. 3 is a schematic diagram of a portion of an atomic layer deposition coating system according to an embodiment;
FIG. 4 is a partial cross-sectional view of an atomic layer deposition coating system;
FIG. 5 is a schematic diagram of blowing a first purge flow of helium and a second purge flow of argon into a process chamber;
FIG. 6 is a schematic diagram of blowing a first purge flow of nitrogen and a second purge flow of argon into a process chamber;
FIG. 7a is a schematic drawing of the blowing of helium gas from a first height H1-1 toward the area to be plated;
FIG. 7b is a pressure split field layout in the process chamber after blowing helium gas from the first height H1-1 and toward the to-be-plated area;
FIG. 8a is a schematic drawing of helium gas blown from a first height H1-2 and toward the area to be plated;
FIG. 8b is a pressure split field layout in the process chamber after blowing helium gas from the first height H1-2 and toward the to-be-plated area;
FIG. 9a is a schematic drawing of helium gas blown from a first height H1-3 and toward the area to be plated;
FIG. 9b is a pressure split field layout in the process chamber after blowing helium gas from the first height H1-3 and toward the to-be-plated area;
FIG. 10a is a schematic view of argon blowing from a second height H2-1 toward the area to be plated;
FIG. 10b is a pressure split field layout in the process chamber after blowing argon gas from the second height H2-1 toward the area to be plated;
FIG. 11a is a schematic view of argon blowing from a second height H2-2 toward the area to be plated;
FIG. 11b is a pressure split field layout in the process chamber after blowing argon gas from the second height H2-2 toward the plating zone;
FIG. 12a is a schematic view of argon blowing from a second height H2-3 toward the area to be plated;
FIG. 12b is a pressure split field layout in the process chamber after blowing argon gas from the second height H2-3 toward the area to be plated;
FIG. 13a is a pressure split field layout in the process chamber after simultaneously blowing helium gas from a first level H1-1 and argon gas from a second level H2-1;
FIG. 13b is a pressure split field layout in the process chamber after simultaneously purging helium gas from the first level H1-2 and argon gas from the second level H2-2;
FIG. 13c is a pressure split field layout in the process chamber after simultaneously blowing helium gas from the first level H1-3 and argon gas from the second level H2-3;
FIG. 14 is a pressure split field layout in the process chamber after simultaneously purging nitrogen from the first height H1-4 and argon from the second height H2-4;
FIG. 15 is a schematic view of oxygen being blown from a first output device within a process chamber;
FIG. 16 is a pressure split field layout of oxygen within a process chamber;
FIG. 17 is a schematic diagram of TMA blown from the second output device within the process chamber;
FIG. 18 is a flow chart of a first growth cycle in one embodiment;
FIG. 19 is a flow chart of a first growth in another embodiment;
FIG. 20 shows the surface drop angle after the native oxide layer is removed from the substrate;
FIG. 21 is a graph showing the surface water droplet angle of the substrate after purging in application example 1;
FIG. 22 is a graph showing the surface water droplet angle of the substrate after purging in application example 2;
FIG. 23 is a graph showing the surface water droplet angle of the substrate after purging in comparative example 1;
FIG. 24 is a graph showing the surface water droplet angle of the substrate after purging in comparative example 2;
FIG. 25 is a plot of the thickness of the film layer on the coated substrate in application example 5;
FIG. 26 is a diagram of the pressure split field in the process chamber after blowing helium and argon from the first height H1-1;
FIG. 27 is a diagram showing the distribution of the pressure distribution field in the process chamber after blowing helium and argon from the first height H1-2;
FIG. 28 is a diagram of the pressure split field layout in the process chamber after blowing helium and argon from the first height H1-3;
FIG. 29 is a pressure distribution field layout in the process chamber after blowing nitrogen and argon from the first height H1-4.
Reference numerals in the drawings are described as follows:
1. a first air stream; 2. a second gas stream;
100. A process chamber; 110. a top side; 120. a bottom side; 130. a first output position; 131. a first vertical projection; 140. a second output position; 141. a second vertical projection; 150. a first airflow output device; 151. a shower head; 152. a first air outlet hole; 160. a second air flow output device; 161. an annular pipe; 162. an air inlet hole; 163. a second air outlet hole; 170. a base; 180. an air suction hole; 190. a workpiece to be plated; 191. and a region to be plated.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. When an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1-4, an embodiment of the present application provides a deposition process for a plasma enhanced atomic layer deposition, wherein the deposition process is performed in a deposition system for a plasma enhanced atomic layer deposition, the deposition system includes a process chamber 100, the process chamber 100 has a top side 110 and a bottom side 120 opposite to each other, a workpiece 190 (e.g., a substrate) to be deposited is disposed in the process chamber 100 and has a region to be deposited disposed upward (toward the top side 110), and a middle region is between the region to be deposited and the top side 110. In this embodiment, the middle region refers to a space in the height direction, and does not strictly define the boundary in the horizontal direction thereof.
Within the process chamber 100, the coating process includes: placing a workpiece 190 to be plated in the process chamber 100; into the process chamber 100, a gas flow is introduced, which comprises a first gas flow 1 and a second gas flow 2, wherein the first gas flow 1 is blown out from the top side 110 and towards the zone to be plated, and the second gas flow 2 is blown out from the middle zone and from the periphery of the zone to be plated towards the zone to be plated.
Specifically, the first air flow 1 is divided into multiple strands, and each output position (first output position 130) in the process chamber 100 corresponds to the area to be plated, that is, the first vertical projection 131 of the first output position 130 corresponds to the area to be plated 191.
The blowing direction of the first air stream 1 is vertically downward. The output position and the direction of the first air flow 1 are favorable for improving the uniformity of the coating film and the integrity of the coating film, and local film defects are avoided.
The second gas flow 2 is divided into a plurality of streams, and the output positions (second output positions 140) of each stream in the process chamber 100 are distributed at intervals in the circumferential direction of the area to be plated, for example, at equal intervals in the circumferential direction. Each second air stream 2 blows downwards and is offset towards the centre of the zone to be plated.
Further, each second gas flow 2 is located at the periphery of the zone to be plated at the position of the second vertical projection 141 of the output position within the process chamber 100. Referring specifically to fig. 2, the output positions of the second air flows 2 in the process chamber 100 are arranged in a circular ring, and the second vertical projection 141 of the circular ring is located at the periphery of the area to be plated. The output position and the direction of the second air flow 2 are favorable for improving the uniformity of the coating film and the integrity of the coating film, and local film defects are avoided.
The output positions and directions of the first air flow 1 and the second air flow 2 are different, and in different stages, on one hand, each air flow can be flexibly used or the first air flow 1 and the second air flow 2 are matched for use, so that the film quality is improved, on the other hand, the output of the first air flow 1 and the output of the second air flow 2 are mutually noninterfered, the reaction risk of the first air flow 1 and the second air flow 2 can be reduced, and the blocking probability of the output position is effectively avoided.
Atomic Layer Deposition (ALD) processes generally consist of a series of half-reactions, each unit cycle comprising a purge phase and a coating phase, the first gas flow 1 comprising, for the different phases, a first purge gas flow and a first coating gas flow, respectively, output by the different phases; the second gas flow 2 comprises a second purge gas flow and a second coating gas flow which are respectively output in different stages.
In the application, each unit cycle comprises a purging stage, a first coating stage and a second coating stage which are respectively implemented before and after the purging stage, wherein in the purging stage, a first purging airflow and a second purging airflow are blown out simultaneously; one of the first coating air flow and the second coating air flow is blown out in the first coating stage, and the other one of the first coating air flow and the second coating air flow is blown out in the second coating stage.
Wherein the following steps are performed during the purge phase:
Providing a first purge flow, the first purge flow being blown out from a first height H1 above the zone 191 to be plated towards the zone 191 to be plated;
providing a second purge flow, the second purge flow being blown out from a second height H2 above the zone 191 to be plated towards the zone 191 to be plated;
wherein the density of the first purge gas flow is less than the density of the second purge gas flow, the first height H1 is greater than the second height H2 relative to the region 191 to be plated.
The density in the present application refers to the mass density, which is related to the relative molecular mass of the gas, and under the same environmental conditions, the larger the relative molecular mass, the larger the density. According to the application, two kinds of purge air with different specific weights are blown out from different heights, when a first purge air with small density is blown out from a first height H1 and a second purge air with large density is blown out from a second height H2 relative to a region to be coated, turbulent flow split fields of heavy particles and light particles can be formed, and compared with the case that two kinds of purge air are blown out from the same height, impurities on the reaction surface, unreacted gases and byproducts generated by reaction can be better cleaned, so that the impurities are introduced into a film layer in a coating stage, and the quality defect of the film layer is avoided.
The specific gravity difference of the two purge streams, the flow rate and the height have a correlation, wherein under the same condition, the larger the relative molecular mass of gas molecules is, the slower the diffusion rate (namely, the smaller the molecular rate is), the smaller the molecular flow rate is, and the larger the pressure is; when two purge streams are blown into the process chamber from different heights at corresponding flow rates, the molecular diffusion rate (molecular flow rate) of each purge stream in the process chamber 100 is affected, and thus the distribution of the pressure split field is affected.
In an embodiment of the present application, the ratio of the density of the first purge gas flow to the density of the second purge gas flow is D1 (i.e., the ratio of the relative molecular mass of the first purge gas flow to the relative molecular mass of the second purge gas flow, if the gas flows are mixed gas flows, the average relative molecular mass of the gas flows is taken), the ratio of the flow rate of the first purge gas flow to the flow rate of the second purge gas flow is D2, the ratio of the first height H1 to the second height H2 is D3, and the ratio of D1, D2 to D3 is (0.1-0.8): (0.9 to 5.6): (1.2-2.2), for example, the ratio of D1, D2 to D3 is (0.1-0.3): (1.4 to 5.6): (1.2-1.3), for example, the ratio of D1, D2 to D3 is (0.6-0.8): (0.9 to 3.8): (1.2-1.4) capable of forming a uniform split flow field in the process chamber 100.
Referring to fig. 5 and 6, the first purge flow may be helium (He) or nitrogen (N 2) and the second purge flow may be argon (Ar). Because the specific gravity difference between the first purge gas flow and the second purge gas flow is larger, two gas flows with different flow rates can be formed, and a turbulent flow split flow field of heavy particles and light particles is formed in the process chamber 100, and can effectively purge the workpiece, the precursor which does not participate in the reaction on the reaction surface and the byproducts generated by the reaction, such as methane, and the like, so that the cleanliness of the surface is improved, and carbon atoms, hydrogen atoms, other unnecessary byproducts and substances in the deposited film layer are effectively reduced.
There is a correlation between the density, flow rate, and height of the two purge streams, and a reasonable fit helps to promote uniformity of the pressure split field within the process chamber 100. For example, referring to FIGS. 7 a-9 b, the flow rate of the first purge gas stream (helium) is 2.8-5.6 cm/s and the flow rate of the second purge gas stream (argon) is 1.0-2.0 cm/s; separately blowing helium gas from a first height H1, wherein the first height H1-1 is 55mm (FIGS. 7a, 7 b), the first height H1-2 is 45mm (FIGS. 8a, 8 b), and the first height H1-3 is 35mm (FIGS. 9a, 9 b); referring to fig. 10 a-12 b, argon is blown out separately from a second height H2, wherein the second height H2-1 is 45mm (fig. 10a, 10 b), the second height H2-2 is 35mm (fig. 11a, 11 b), and the second height H2-3 is 25mm (fig. 12a, 12 b). FIGS. 7b, 8b, and 9b are, respectively, pressure split field layouts of the process chamber after separately blowing helium gas from different first heights, and FIGS. 10b, 11b, and 12b are, respectively, pressure split field layouts of the process chamber after separately blowing argon gas from different second heights.
Referring to fig. 13 a-13 c, helium and argon are blown out from the first height H1 and the second height H2 respectively, wherein fig. 13a shows that a relatively uniform flow-dividing field is formed in the process chamber 100 after helium is blown out from the first height H1-1 (55 mm) and argon is blown out from the second height H2-1 (45 mm); FIG. 13b shows a uniform split field pattern formed within the process chamber 100 after helium gas is purged from a first height H1-2 (45 mm) and argon gas is purged from a second height H2-2 (35 mm); FIG. 13c shows a more uniform split field pattern formed within the process chamber 100 after helium gas is purged from a first height H1-3 (35 mm) and argon gas is purged from a second height H2-3 (25 mm). FIG. 14 shows that a uniform flow-dividing field is formed in the process chamber 100 after simultaneously blowing nitrogen gas (flow rate of 1.87-3.73 cm/s) from the first height H1-4 (45 mm) and argon gas (flow rate of 1.0-2.0 cm/s) from the second height H2-4 (35 mm).
In the prior art, a first purge flow and a second purge flow are simultaneously blown from the top side, for example, fig. 26 is a pressure split flow field layout formed in the process chamber after helium and argon are blown from a first height H1-1 (55 mm). FIG. 27 is a pressure distribution field layout of helium and argon blown from a first height H1-2 (45 mm) formed in a process chamber. FIG. 28 is a pressure distribution field layout formed in the process chamber after blowing helium and argon from a first height H1-3 (35 mm). FIG. 29 is a pressure distribution field layout formed in the process chamber after blowing nitrogen and argon from a first height H1-4 (45 mm). Compared with the prior art, the application blows out each sweeping air flow from different output positions and different directions, and can improve the uniformity of pressure distribution in the process cavity.
In one embodiment, the flow ratio of the first purge gas flow to the second purge gas flow is 1 (1-3), preferably 1 (1-2), and more preferably 1 (1.3-2). The total flow rate of the purging is 300-400 sccm, preferably 300-350 sccm.
The temperature for implementing the purging condition is 150-250 ℃, preferably 200 ℃; the bottom pressure in the process chamber 100 is 5.5X10 - 6 Torr, and the working pressure is 300 to 600Torr, preferably 500Torr. The purging time is 5-10 s, for example 5s.
Referring to fig. 15-17, the first coating gas flow includes an oxygen precursor and the second coating gas flow includes an aluminum precursor; the oxygen precursor is, for example, oxygen gas, and the aluminum precursor is, for example, trimethylaluminum (TMA). The first coating air flow and the second coating air flow are output from different positions, so that the risk of reaction of the two coating air flows at the output positions can be effectively reduced, and further, the influence on the quality of the film layer due to the fact that a plurality of impurities are introduced into the film layer is avoided.
The flow of the oxygen precursor in the first film plating airflow is 200-250 sccm; the fluid pressure of the aluminum precursor in the second coating airflow is 0.3-0.5 kg/cm 2. The first coating gas stream and the second coating gas stream each further comprise a carrier gas, such as argon.
When the first coating air flow is blown out, the reaction conditions in the process chamber 100 are as follows: the temperature is 150-250 ℃, preferably 200 ℃; the bottom pressure was 5.5X10 -6 Torr, the operating pressure was 1.0Torr, and the operating time was 5s. When the second coating air flow is blown out, the reaction conditions in the process chamber 100 are as follows: the temperature is 150-250 ℃, preferably 200 ℃; the bottom pressure was 5.5X10 -6 Torr, the operating pressure was 10 Torr, and the operating time was 5s. Further, the first plating gas flow or the second plating gas flow can be blown out under the plasma condition, and the plasma power is 70-100W, preferably 80W.
Referring to the embodiment shown in fig. 18, the plating process includes depositing a film layer on the surface of the workpiece to be plated through a plurality of growth cycles, wherein the first growth cycle includes a first plating stage, a first purge stage, a second plating stage, and a second purge stage that are sequentially performed; wherein a second coating gas flow, for example, a second coating gas flow containing an aluminum precursor (TMA), is blown out at the first coating stage, see fig. 18 (b); blowing a first purge gas flow (e.g., helium) and a second purge gas flow (e.g., argon) during a first purge phase, see fig. 18 (c); blowing a first coating gas flow, e.g., of an oxygen-containing precursor, during the second coating stage, see fig. 18 (d); a first purge gas stream (e.g., helium) and a second purge gas stream (e.g., argon) are blown out during the second purge phase, see fig. 18 (e). Further, the first purge flow and the second purge flow are blown out simultaneously.
Referring to fig. 19, in another embodiment, the first growth cycle includes a first plating stage, a first purge stage, a second plating stage, and a second purge stage performed in sequence, wherein a first plating gas flow, such as a first plating gas flow of an oxygen-containing precursor, is blown out during the first plating stage, see fig. 19 (b); blowing a first purge gas flow (e.g., helium) and a second purge gas flow (e.g., argon) during a first purge phase, see fig. 19 (c); blowing a second coating gas flow, for example, a second coating gas flow containing an aluminum precursor (TMA), in a second coating stage, see fig. 19 (d); a first purge gas stream (e.g., helium) and a second purge gas stream (e.g., argon) are blown out during the second purge phase, see fig. 19 (e).
The plating process also includes pre-purging the workpiece to be plated in the process chamber prior to performing the first growth cycle, see, for example, fig. 18 (a) and 19 (a). The pre-purge includes blowing a first pre-purge gas stream and a second pre-purge gas stream through a first output location 130 and a second output location 140, respectively. The first pre-purge gas stream may be helium and/or nitrogen and the second pre-purge gas stream may be argon. In the pre-sweep stage, the first pre-sweep gas stream and the second pre-sweep gas stream are blown out simultaneously to rapidly form a uniform split flow field.
Typically, the workpiece 190 to be plated is pre-treated, including surface cleaning and removal of surface native oxide, and then placed in the process chamber 100.
The second purge gas flow and the second plating gas flow may share an output position, or may be output from different output positions, for example, the output positions of the second purge gas flow and the second plating gas flow in the circumferential direction are different.
The coating process may further include pumping air from the bottom side 120 of the process chamber 100, such as by creating a pumping vent in the bottom wall of the process chamber 100. During the purge phase, the evacuation from the bottom side 120 can create a better purge flow field, which is advantageous for efficient removal of impurities and reaction byproducts within the process chamber 100.
The total pumping rate is 10 to 30 Pa.m 3/s, preferably 15 to 25 Pa.m 3/s, more preferably 20 Pa.m 3/s. Further, when the purging is performed, the process chamber 100 is simultaneously evacuated through the plurality of evacuation holes 180, and the evacuation rate of the single evacuation hole 180 is 0.85 Pa ·m 3/s.
In different stages, the heights of the output positions of the first air flow 1 and the second air flow 2 relative to the to-be-plated area in the process chamber 100 are adjustable, so that the adjustment is convenient according to the actual plating process, and a better plating effect is achieved.
Referring to fig. 1 to 4, in order to implement the above-mentioned coating process, the present application provides a plasma enhanced ald coating system, and the process chamber 100 includes a base 170, a first air flow output device 150 and a second air flow output device 160; wherein the base 170 is used for supporting a workpiece 190 to be plated; the first air flow output device 150 is located at a first height H1 above the area to be plated, and is used for blowing the first air flow 1 towards the area to be plated; the second air flow output device 160 is located at a second height H2 above the area to be plated, and the first height H1 is greater than the second height H2, that is, the second air flow output device 160 is located in the middle area, and the second air flow output device 160 is used for blowing the second air flow 2 from the periphery of the area to be plated and toward the area to be plated.
Specifically, the first airflow output device 150 includes a shower head 151, where the shower head 151 has first air outlet holes 152 arranged at intervals, and a first nozzle is disposed in each first air outlet hole 152. In order to blow the first air flow 1 vertically toward the area to be plated, the air outlet direction of the first nozzle is arranged vertically downward.
In one embodiment, the diameter of the shower head is 250-320 mm, and the aperture of the air outlet hole of the first nozzle is 0.3-1 mm; the number of the first air outlet holes is 3000-4000, for example 3500.
To facilitate the controlled delivery of each gas flow, the first gas flow output 150 is configured with a first delivery conduit and a first valve for selectively delivering either a first coating gas flow or a first purge gas flow to the first delivery conduit.
The second air flow output device 160 includes an annular pipe 161, the annular pipe 161 has an inner wall and an outer wall distributed along a radial direction, wherein the outer wall is provided with an air inlet 162, the inner wall is provided with second air outlet 163 arranged at intervals, the second air outlet 163 is provided with a second nozzle, and a radial gap between the inner wall and the outer wall provides an air flow channel. The second air outlet 163 may be in the shape of a circular hole, and has a hole diameter of 1 to 5mm, preferably 1 to 3mm, and more preferably 1mm, and the hole diameter is in favor of controlling air flow and stronger air pressure.
The annular duct 161 of different sizes should be provided with a suitable number of second air outlet holes 163, and an excessive number of holes would result in a slow gas flow rate and an excessive number of holes would result in an excessively fast gas flow rate, both of which would affect the distribution uniformity of the split flow field. In one embodiment, the outer diameter of the annular pipe 161 is 200-320 mm, and the number of the second air outlet holes 163 is 12-18.
To facilitate controlled delivery of each gas flow, the second gas flow output 160 is configured with a second conduit and a second valve for selectively delivering a second coating gas flow or a second purge gas flow to the second conduit.
Further, the second gas outlet holes 163 are divided into two groups, and each group is independently provided with a conveying pipeline for conveying the second purge gas flow and the second coating gas flow.
In one embodiment, the first height H1 is 30-50 mm, preferably 40-50 mm, and more preferably 45mm; the second height H2 is 20 to 40mm, preferably 30 to 40mm, and more preferably 35mm.
In one embodiment, the bottom sidewall of the process chamber 100 is provided with an air vent 180. The suction holes 180 may be provided in plurality and arranged at intervals in the circumferential direction. Further, the diameter of the bottom of the process chamber 100 is 250-350 mm, and the number of the pumping holes 180 may be 18-24.
The base 170 is a liftable structure, and the relative height of the workpiece 190 to be plated relative to the first air flow output device 150 and the second air flow output device 160 is adjusted by lifting the base 170.
The plasma enhanced atomic layer deposition coating process and the plasma enhanced atomic layer deposition coating system provided by the application can be used for preparing chips so as to improve the quality of the chips.
The application is further described below in connection with specific process parameters, but the application is not limited thereto.
The heights of the first air flow output device and the second air flow output device in the application examples 1 to 8 and the comparative examples 1 to 4 are 45mm and 35mm respectively relative to the substrate.
Application example 1
Removing a surface primary oxide layer on a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5X10 -6 Torr, introducing helium and argon into the process Cheng Qiangna at the temperature of 200 ℃, wherein the helium is vertically blown out from a shower head of a first airflow output device towards the substrate, the argon is blown out from a second airflow output device towards the lower side, the flow ratio of the argon to the helium is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr. Wherein the flow rate of helium is 3.36cm/s and the flow rate of argon is 1.8cm/s.
Application example 2
Removing a surface primary oxide layer on a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5X10 -6 Torr, introducing nitrogen and argon into the process Cheng Qiangna at the temperature of 200 ℃, wherein the nitrogen is vertically blown out from a shower head of a first airflow output device towards the substrate, the argon is blown out from a second airflow output device towards the lower side, the flow ratio of the argon to the nitrogen is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr. Wherein the flow rate of nitrogen is 3.36cm/s and the flow rate of argon is 1.8cm/s.
Comparative example 1
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, introducing helium and argon into a system Cheng Qiangna at the temperature of 200 ℃, wherein the helium and the argon are vertically blown out from a shower head of a first airflow output device towards the substrate, the flow ratio of the argon to the helium is 3:2, the total flow is 300sccm, the purging time is 7s, and the working pressure is 500Torr. Wherein the flow rate of helium is 3.36cm/s and the flow rate of argon is 1.8cm/s.
Comparative example 2
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, and introducing nitrogen and argon into a process Cheng Qiangna at the temperature of 200 ℃, wherein the nitrogen and the argon are vertically blown out from a shower head of a first airflow output device, the flow ratio of the argon to the nitrogen is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr. Wherein the flow rate of nitrogen is 3.36cm/s and the flow rate of argon is 1.8cm/s.
The surface water drop angle after removal of the native oxide layer of the substrate and the surface water drop angle after completion of purging were measured for the substrates used in examples 1 and 2 and comparative examples 1 and 2, and the surface cleanliness was analyzed by the surface water drop angle, and generally the smaller the surface water drop angle, the higher the cleanliness.
As a result of the test, referring to fig. 20 to 24, the surface water drop angle of the substrate after the native oxide layer is removed is 72 °, the surface water drop angle of the substrate after the purging in application example 1 is 44.3 °, the surface water drop angle of the substrate after the purging in application example 2 is 48.7 °, the surface water drop angle of the substrate after the purging in comparative example 1 is 58.8 °, and the surface water drop angle of the substrate after the purging in comparative example 2 is 52.3 °, which indicates that helium and argon are blown out from different output positions and directions, and is favorable for improving the cleanliness of the substrate surface.
Application example 3
(1) Pre-purge
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, enabling helium and argon to pass through the process cavity at the temperature of 200 ℃, wherein the helium is vertically blown out from a shower head of a first airflow output device, the argon is blown out downwards from a second airflow output device, the flow ratio of the argon to the helium is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2) First growth cycle
(2A) Pumping the film coating system to make the pressure below 5.5 multiplied by 10 -6 Torr, and vertically introducing TMA precursor and argon gas into the film coating system Cheng Qiangna from a shower head of the first gas flow output device, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2b) The film plating system is pumped and heated to enable the pressure to be below 5.5X10 -6 Torr and the temperature to be 200 ℃, helium and argon are passed into the process cavity, wherein the helium is vertically blown out from a shower head of the first airflow output device, the argon is blown out downwards from the second airflow output device, the flow ratio of the argon to the helium is 2:1, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2c) Pumping and heating the film coating system to enable the pressure to be lower than 5.5 multiplied by 10 -6 Torr, introducing oxygen and argon into the film forming device Cheng Qiangna from a shower head vertical output device of the first air flow, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, starting plasma, maintaining the pressure at 1.0Torr, the plasma power is 80W, the working time is 5s, and depositing an oxide layer on the surface of the substrate;
(2d) And pumping and heating the film coating system to enable the pressure to be lower than 5.5X10 -6 Torr and the temperature to be 200 ℃, and enabling helium and argon to pass through the process chamber, wherein the helium is vertically blown out from a shower head of the first airflow output device, the argon is blown out downwards from the second airflow output device, the flow ratio of the argon to the helium is 2:1.5, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr.
(3) Repeating the first circulation step for 302 times to obtain the film with the thickness of 50nm on the film-coated substrate.
Wherein the flow rate of helium in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of helium in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of helium in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
Application example 4
(1) Pre-purge
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5X10 -6 Torr, enabling nitrogen and argon to pass through the process cavity at the temperature of 200 ℃, wherein the nitrogen is vertically blown out from a shower head of a first air flow output device, the argon is blown out downwards from a second air flow output device, the flow ratio of the argon to the nitrogen is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2) First growth cycle
(2A) Pumping the film coating system to make the pressure below 5.5 multiplied by 10 -6 Torr, and introducing TMA precursor and argon gas into the film coating system Cheng Qiangna from a shower head vertical output device of the first air flow, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2b) The film plating system is pumped and heated to enable the pressure to be below 5.5X10 -6 Torr and the temperature to be 200 ℃, nitrogen and argon are passed into the process cavity, wherein the nitrogen is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the nitrogen is 2:1, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2c) The film plating system is pumped and heated to enable the pressure to be lower than 5.5 multiplied by 10 -6 Torr, oxygen and argon are vertically introduced into the film plating system Cheng Qiangna from a shower head of the first airflow output device, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, plasma is started, the pressure is maintained at 1.0Torr, the plasma power is 80W, the working time is 5s, and an oxide layer is deposited on the surface of the substrate;
(2d) And (3) pumping and heating the film coating system to enable the pressure to be lower than 5.5X10 -6 Torr, enabling the temperature to be 200 ℃, enabling nitrogen and argon to pass through the process chamber, wherein the nitrogen is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the nitrogen is 2:1.5, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr.
(3) Repeating the first circulation step for 302 times to obtain the film with the thickness of 50nm on the film-coated substrate.
Wherein the flow rate of nitrogen in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of nitrogen in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of nitrogen in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
Application example 5
(1) Pre-purge
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5X10 -6 Torr, introducing helium and argon into the process Cheng Qiangna at the temperature of 200 ℃, wherein the helium is vertically blown out from a shower head of a first airflow output device, the argon is blown out downwards from a second airflow output device, the flow ratio of the argon to the helium is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2) First growth cycle
(2A) Pumping the film coating system to make the pressure below 5.5 multiplied by 10 -6 Torr, and introducing TMA precursor and argon gas into the film coating system Cheng Qiangna from a second gas flow output device, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2b) Pumping and heating the film coating system to enable the pressure to be below 5.5X10 -6 Torr and the temperature to be 200 ℃, and introducing helium and argon into the film coating system Cheng Qiangna, wherein the helium is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the helium is 2:1, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2c) Pumping and heating the film coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, introducing oxygen and argon into the film forming device Cheng Qiangna from a first airflow output device, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, starting plasma, maintaining the pressure at 1.0Torr, the power of the plasma is 80W, the working time is 5s, and depositing an oxide layer on the surface of the substrate;
(2d) And pumping and heating the film coating system to enable the pressure to be lower than 5.5X10 -6 Torr, and introducing helium and argon into the film coating system Cheng Qiangna at the temperature of 200 ℃, wherein the helium is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the helium is 2:1.5, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr.
(3) Repeating the first growth cycle for 302 times to obtain a film with a thickness of 50nm on the coated substrate.
Wherein the flow rate of helium in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of helium in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of helium in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
Each film thickness and uniformity were tested and the results are shown in fig. 25 and table 1:
TABLE 1 thickness distribution table
Application example 6
(1) Pre-purge
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5X10 -6 Torr, and introducing nitrogen and argon into the process Cheng Qiangna at the temperature of 200 ℃, wherein the nitrogen is vertically blown out from a shower head of a first air flow output device, the argon is blown out downwards from a second air flow output device, the flow ratio of the argon to the nitrogen is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2) First growth cycle
(2A) Pumping the film coating system to make the pressure below 5.5 multiplied by 10 -6 Torr, and introducing TMA precursor and argon gas into the film coating system Cheng Qiangna from a second gas flow output device, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2b) Pumping and heating the film coating system to enable the pressure to be below 5.5X10 -6 Torr and the temperature to be 200 ℃, and introducing nitrogen and argon into the film coating system Cheng Qiangna, wherein the nitrogen is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the nitrogen is 2:1, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2c) Pumping and heating the film coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, introducing oxygen and argon into the film forming device Cheng Qiangna from a first airflow output device, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, starting plasma, maintaining the pressure at 1.0Torr, the power of the plasma is 80W, the working time is 5s, and depositing an oxide layer on the surface of the substrate;
(2d) And (3) pumping and heating the film coating system to enable the pressure to be lower than 5.5X10 -6 Torr, and introducing nitrogen and argon into the film coating system Cheng Qiangna at the temperature of 200 ℃, wherein the nitrogen is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the nitrogen is 2:1.5, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr.
(3) Repeating the first growth cycle for 302 times to obtain a film with a thickness of 50nm on the coated substrate.
Wherein the flow rate of nitrogen in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of nitrogen in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of nitrogen in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
Application example 7
(1) Pre-purge
Removing a surface primary oxide layer on a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5X10 -6 Torr, introducing helium and argon into the process Cheng Qiangna at the temperature of 200 ℃, wherein the helium is vertically blown out from a shower head of a first airflow output device, the argon is blown out downwards from a second airflow output device, the flow ratio of the argon to the helium is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr.
(2) First growth cycle
(2A) Pumping and heating the film coating system to enable the pressure to be lower than 5.5 multiplied by 10 -6 Torr and the temperature to be 200 ℃, introducing oxygen and argon into the film coating system Cheng Qiangna from a first airflow output device, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, starting plasma, maintaining the pressure at 1.0Torr, the power of the plasma is 80W, the working time is 5s, and depositing an oxide layer on the surface of a substrate;
(2b) Pumping the film coating system, enabling the pressure to be lower than 5.5 multiplied by 10 -6 Torr, and introducing helium and argon into the film coating system Cheng Qiangna, wherein the helium is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the helium is 2:1, the total flow is 300sccm, the blowing time is 3s, and the working pressure is 500Torr;
(2c) Pumping and heating the film coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, and introducing TMA precursor and argon gas into the film coating system Cheng Qiangna from a second gas flow output device, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2d) And pumping the film coating system to enable the pressure to be lower than 5.5 multiplied by 10 -6 Torr, and introducing helium and argon into the film coating system Cheng Qiangna at the temperature of 200 ℃, wherein the helium is vertically blown out from a shower head of the first airflow output device, the argon is blown out downwards from the second airflow output device, the flow ratio of the argon to the helium is 2:1.5, the total flow is 300sccm, the blowing time is 3s, and the working pressure is 500Torr.
(3) Repeating the first growth cycle for 302 times to obtain a film with a thickness of 50nm on the coated substrate.
Wherein the flow rate of nitrogen in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of nitrogen in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of nitrogen in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
Application example 8
(1) Pre-purge
Removing a surface primary oxide layer on a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5X10 -6 Torr, introducing nitrogen and argon into the process Cheng Qiangna at the temperature of 200 ℃, wherein the nitrogen is vertically blown out from a shower head of a first air flow output device, the argon is blown out downwards from a second air flow output device, the flow ratio of the argon to the nitrogen is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr.
(2) First growth cycle
(2A) Pumping and heating the film coating system to enable the pressure to be lower than 5.5 multiplied by 10 -6 Torr and the temperature to be 200 ℃, introducing oxygen and argon into the film coating system Cheng Qiangna from a first airflow output device, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, starting plasma, maintaining the pressure at 1.0Torr, the power of the plasma is 80W, the working time is 5s, and depositing an oxide layer on the surface of a substrate;
(2b) Pumping the film coating system to enable the pressure to be below 5.5X10 -6 Torr and the temperature to be 200 ℃, and introducing nitrogen and argon into the film coating system Cheng Qiangna, wherein the nitrogen is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the nitrogen is 2:1, the total flow is 300sccm, the blowing time is 3s, and the working pressure is 500Torr;
(2c) Pumping and heating the film coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, and introducing TMA precursor and argon gas into the film coating system Cheng Qiangna from a second gas flow output device, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2d) And (3) pumping and heating the film coating system to enable the pressure to be lower than 5.5X10 -6 Torr, and introducing nitrogen and argon into the film coating system Cheng Qiangna at the temperature of 200 ℃, wherein the nitrogen is vertically blown out from a shower head of the first air flow output device, the argon is blown out downwards from the second air flow output device, the flow ratio of the argon to the nitrogen is 2:1.5, the total flow is 300sccm, the blowing time is 3s, and the working pressure is 500Torr.
(3) Repeating the first growth cycle for 302 times to obtain a film with a thickness of 50nm on the coated substrate.
Wherein the flow rate of nitrogen in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of nitrogen in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of nitrogen in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
Comparative example 3
(1) Pre-purge
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, introducing helium and argon into a process Cheng Qiangna at the temperature of 200 ℃, vertically blowing out the mixed helium and argon from a shower head of a first airflow output device, wherein the flow ratio of the argon to the helium is 3:2, the total flow is 300sccm, the blowing time is 7s, and the working pressure is 500Torr;
(2) First growth cycle
(2A) Pumping the film coating system to make the pressure below 5.5 multiplied by 10 -6 Torr, and introducing TMA precursor and argon gas into the film coating system Cheng Qiangna through a first gas flow output device, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2b) Pumping and heating the film coating system to enable the pressure to be below 5.5X10 -6 Torr and the temperature to be 200 ℃, and introducing helium and argon into the film coating system Cheng Qiangna through a first airflow output device, wherein the flow ratio of the argon to the helium is 2:1, the total flow is 300sccm, the purging time is 7s, and the working pressure is 500Torr;
(2c) Pumping and heating the film coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, introducing oxygen and argon into the film forming device Cheng Qiangna through a first airflow output device, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, starting plasma, maintaining the pressure at 1.0Torr, the power of the plasma is 80W, the working time is 5s, and depositing an oxide layer on the surface of the substrate;
(2d) And pumping and heating the film coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, wherein the temperature is 200 ℃, and introducing helium and argon into the film coating system Cheng Qiangna through a first airflow output device, wherein the flow ratio of the argon to the helium is 2:1.5, the total flow is 300sccm, the purging time is 7s, and the working pressure is 500Torr.
(3) Repeating the first growth cycle for 302 times to obtain a film with a thickness of 50nm on the coated substrate.
Wherein the flow rate of helium in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of helium in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of helium in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
Film thickness was measured and the results are shown in Table 2:
TABLE 2 thickness distribution table
Compared with comparative example 3, the maximum difference of the film layers in application example 5 is 4.402 a, and the maximum difference of the film layers in comparative example 3 is 7.689 a, which indicates that changing TMA from being blown out of the second air flow output device can avoid defects caused by introducing impurities into the film layers and ensure uniformity of the film layers.
Comparative example 4
(1) Pre-purge
Removing a surface primary oxide layer from a substrate in advance, placing the substrate in a process cavity, pumping and heating a coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, introducing nitrogen and argon into the substrate Cheng Qiangna through a first airflow output device, wherein the flow ratio of the argon to the nitrogen is 3:2, the total flow is 300sccm, the purging time is 7s, and the working pressure is 500Torr;
(2) First growth cycle
(2A) Pumping the film coating system to make the pressure below 5.5 multiplied by 10 -6 Torr, and introducing TMA precursor and argon gas into the film coating system Cheng Qiangna through a first gas flow output device, wherein the fluid flow of the TMA precursor is 0.3kg/cm 2, the argon gas flow is 20sccm, the working time is 5s, and the working pressure is 10Torr;
(2b) Pumping and heating the film coating system to enable the pressure to be below 5.5X10 -6 Torr and the temperature to be 200 ℃, and introducing nitrogen and argon into the film coating system Cheng Qiangna through a first air flow output device, wherein the flow ratio of the argon to the nitrogen is 2:1, the total flow is 300sccm, the purging time is 7s, and the working pressure is 500Torr;
(2c) Pumping and heating the film coating system to enable the pressure to be below 5.5 multiplied by 10 -6 Torr, introducing oxygen and argon into the film forming device Cheng Qiangna through a first airflow output device, wherein the flow of the oxygen is 200sccm, the flow of the argon is 20sccm, starting plasma, maintaining the pressure at 1.0Torr, the power of the plasma is 80W, the working time is 5s, and depositing an oxide layer on the surface of the substrate;
(2d) And (3) pumping and heating the film coating system to enable the pressure to be lower than 5.5 multiplied by 10 -6 Torr, wherein the temperature is 200 ℃, and introducing nitrogen and argon into the film coating system Cheng Qiangna through a first gas flow output device, wherein the flow ratio of the argon to the nitrogen is 2:1.5, the total flow is 300sccm, the purging time is 7s, and the working pressure is 500Torr.
(3) Repeating the first growth cycle for 302 times to obtain a film with a thickness of 50nm on the coated substrate.
Wherein the flow rate of nitrogen in the step (1) is 3.36cm/s, the flow rate of argon is 1.8cm/s, the flow rate of nitrogen in the step (2 b) is 2.8cm/s, the flow rate of argon is 2cm/s, the flow rate of nitrogen in the step (2 d) is 3.64cm/s, and the flow rate of argon is 1.7cm/s.
The surface densities of the film layers on the film coated substrates of examples 3 to 8 and comparative examples 3 and 4 and the moisture blocking rate of the test film coated substrates were calculated by the measured surface roughness RMS, and the water condition of the test film coated substrates of the present application was 40 ℃ and 70% absolute humidity.
Wherein the surface density formula is:
ρ=1/{ rms× (10 -7)-2 }; in nm/cm -2.
TABLE 3 results of surface roughness, surface Density and moisture blocking Rate
The test results are shown in Table 3, the application adopts the water-gas barrier rate (the unit is g/m 2/d, namely g/square meter/day) to measure, and the smaller the water-gas barrier rate, the better the barrier effect of the film layer on water-gas is.
The coating process provided by the application blows out each air flow from different output positions and directions, and can reduce the risks of output blockage and impurity introduction into the film layer, thereby being beneficial to improving the quality of the film layer.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of the application should be assessed as that of the appended claims.
Claims (10)
1. A process for plasma enhanced atomic layer deposition, comprising:
Placing a workpiece to be plated in a process cavity, wherein the process cavity is provided with a top side and a bottom side which are opposite, the workpiece to be plated is provided with a region to be plated facing the top side, and a middle region is arranged between the region to be plated and the top side;
Introducing an air flow into the process chamber, the air flow comprising a first air flow and a second air flow, the first air flow being blown out from the top side and toward the zone to be plated, the second air flow being blown out from the middle region and from the periphery of the zone to be plated toward the zone to be plated.
2. The coating process of claim 1, wherein the first gas flow is divided into a plurality of streams, and each stream has an output position in the process chamber corresponding to a region to be coated;
The first air flow is blown vertically downwards towards the area to be plated.
3. The coating process of claim 1, wherein the second gas flow is divided into a plurality of streams, and the output positions of each stream in the process chamber are distributed at intervals in the circumferential direction of the region to be coated;
Each second air stream blows downwards and is offset towards the center of the area to be plated.
4. A coating process according to claim 3, wherein the vertical projection of the output position of each second gas flow in the process chamber is at the periphery of the area to be coated.
5. A coating process according to claim 3, wherein the output positions of the second gas flows in the process chamber are arranged in a circular ring.
6. The coating process of claim 1, wherein the height of each gas flow in the process chamber relative to the output position of the coating zone is adjustable.
7. The plating process according to claim 1, further comprising: air is pumped from the bottom side of the process chamber.
8. The plating process according to claim 1, wherein the first gas flow includes a first purge gas flow and a first plating gas flow outputted from different stages, respectively;
the second air flow comprises a second sweeping air flow and a second coating air flow which are respectively output in different stages.
9. The coating process of claim 8, comprising a purge stage and first and second coating stages respectively performed before and after the purge stage, wherein:
during the purge phase, the first purge gas stream is blown out simultaneously with the second purge gas stream;
And blowing one of the first coating air flow and the second coating air flow in the first coating stage, and blowing the other of the first coating air flow and the second coating air flow in the second coating stage.
10. The coating process of claim 9, wherein the first purge gas stream is helium and/or nitrogen and the second purge gas stream is argon;
the first coating gas stream includes an oxygen precursor and the second coating gas stream includes an aluminum precursor.
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| CN202558934U (en) * | 2012-05-28 | 2012-11-28 | 天威新能源控股有限公司 | High-uniformity silane spray device for OTB coating equipment |
| CN214991834U (en) * | 2021-06-16 | 2021-12-03 | 南京港锐电子科技有限公司 | Plasma enhanced atomic layer deposition equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN202558934U (en) * | 2012-05-28 | 2012-11-28 | 天威新能源控股有限公司 | High-uniformity silane spray device for OTB coating equipment |
| CN214991834U (en) * | 2021-06-16 | 2021-12-03 | 南京港锐电子科技有限公司 | Plasma enhanced atomic layer deposition equipment |
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