CN115595561A - Plasma enhanced atomic layer deposition equipment and deposition method - Google Patents
Plasma enhanced atomic layer deposition equipment and deposition method Download PDFInfo
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- CN115595561A CN115595561A CN202211346014.XA CN202211346014A CN115595561A CN 115595561 A CN115595561 A CN 115595561A CN 202211346014 A CN202211346014 A CN 202211346014A CN 115595561 A CN115595561 A CN 115595561A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides plasma enhanced atomic layer deposition equipment and a deposition method. The deposition equipment comprises a first conduit and a second conduit, wherein the first conduit and the second conduit are used for separating the metal precursor from the carrier gas, on one hand, only the metal precursor passes through the first conduit, and due to the self-limiting reaction of a metal source, a film layer cannot be further deposited, so that the aim of keeping a discharge area clean can be fulfilled; on the other hand, the sleeve design can protect the first conduit from being ignited and further protect the metal source from being ionized, because the electric field generated by the discharge device is greatly lost when passing through the deposition cavity, and once the carrier gas in the deposition cavity is ionized, the plasma is similar to fluid metal and can quickly offset the electric field, so that the electric field effect in the first conduit is further reduced, and no coating film remains; the deposition equipment of the invention can still keep the inner wall of the discharge area clean under the condition that the discharge device continuously discharges.
Description
Technical Field
The invention relates to the technical field of atomic layer deposition, in particular to plasma enhanced atomic layer deposition equipment and a deposition method.
Background
The atomic layer deposition technology has irreplaceable status in the field of nano coating with excellent coating uniformity, conformality and film thickness controllability, and the traditional atomic layer deposition is realized in a thermal deposition mode: and alternately introducing the precursor gas into a reaction chamber heated to a certain temperature, and alternately reacting after being heated and decomposed to realize the atomic-level solid coating. In addition, the method can also decompose the precursor by utilizing a mode of generating low-temperature plasma by glow discharge, greatly enhance the chemical activity of reaction substances at lower temperature and further realize coating, is called as a plasma enhanced atomic layer deposition technology, can reduce the temperature required by ALD (atomic layer deposition), provides possibility for coating on a heat-sensitive material and can also realize coating processes which cannot be realized only by thermal deposition ALD.
However, in the conventional PEALD process, the residual metal source in the tube is still inevitably ionized under an external voltage, so that part of the metal source and the carrier gas are directly deposited in the discharge region and cannot reach the reaction chamber, on one hand, a large number of light-tight film layers are deposited on the tube wall, the visibility of the tube wall is greatly reduced, and on the other hand, the deposition efficiency of the metal source is reduced. In addition, after the metal precursor is replaced, the thin film material deposited on the inner wall of the quartz tube in the discharge area in the last time is in danger of being bombarded by plasma and polluting the next deposition.
Based on the defects of the current atomic layer deposition, there is a need for improvement.
Disclosure of Invention
In view of the above, the present invention provides a plasma enhanced atomic layer deposition apparatus and a deposition method, so as to solve the defects in the prior art.
In a first aspect, the present invention provides a plasma enhanced atomic layer deposition apparatus comprising:
the deposition cavity is internally provided with a sample table;
the first guide pipe is positioned in the deposition cavity, one end of the first guide pipe is close to the sample table, and the other end of the first guide pipe extends upwards and penetrates out of the deposition cavity;
a second conduit in communication with the deposition chamber;
and the discharge device is positioned outside the deposition cavity and is used for ionizing the carrier gas entering the deposition cavity through the second conduit.
Preferably, the plasma enhanced atomic layer deposition device is characterized in that a heating device is arranged on the deposition cavity corresponding to the sample stage and used for heating the sample stage.
Preferably, the plasma enhanced atomic layer deposition device is characterized in that a first vacuum pumping system is arranged outside the deposition cavity and used for vacuumizing the deposition cavity.
Preferably, the plasma enhanced atomic layer deposition device further comprises a pre-loading cavity, the pre-loading cavity is communicated with the deposition cavity through a gate valve, a pre-loading table is arranged in the pre-loading cavity and used for bearing a substrate to be deposited, and a mechanical conveying device is further arranged in the pre-loading cavity and used for conveying the substrate to be deposited on the pre-loading table to the sample table.
Preferably, plasma reinforcing atomic layer deposition equipment, still include deposit support and pre-load cavity, the deposit cavity install in on the deposit support, pre-load cavity one end with deposit cavity intercommunication, pre-load cavity with the junction of deposit cavity is sealed through the sealing washer, and the slide valve is located in the pre-load cavity, pre-load cavity is located the slide valve top is equipped with brokenly empty valve, pre-load cavity is located the slide valve below is equipped with the vacuum gauge, still be equipped with second vacuum pumping system and quick-open door on the pre-load cavity, be equipped with the transfer lever in the pre-load cavity, the transfer lever top is equipped with the sample platform, the transfer lever is used for conveying the sample platform to the deposit cavity from pre-load cavity.
Preferably, the first conduit and the second conduit of the plasma enhanced atomic layer deposition device are both provided with electromagnetic valves;
the sample stage comprises a sample support and an object stage arranged on the sample support, wherein one side of the object stage is obliquely arranged, and an included angle between one side of the object stage and the horizontal plane is 0-120 degrees.
Preferably, the plasma enhanced atomic layer deposition device, the discharge device includes a conductive coil wrapped outside the deposition chamber;
or, the discharge device comprises parallel electrodes positioned outside the deposition cavity.
Preferably, in the plasma enhanced atomic layer deposition apparatus, the pre-loading chamber and the deposition chamber are both horizontally arranged or vertically arranged;
the deposition cavity body is made of quartz glass corresponding to the position of the discharge device;
the pre-loading cavity is made of stainless steel;
the end of the first conduit outside the deposition cavity is provided with a plurality of inlets.
Preferably, in the plasma-enhanced atomic layer deposition apparatus, one end of the first conduit close to the sample stage is communicated with a gas distributor, the gas distributor is hollow, and a plurality of vent holes are formed in one end face of the gas distributor far away from the first conduit.
In a second aspect, the present invention also provides a plasma enhanced atomic layer deposition method, comprising the steps of:
providing the plasma enhanced atomic layer deposition equipment;
placing the base material to be deposited on a sample table, vacuumizing a deposition cavity, introducing carrier gas into the deposition cavity through a second conduit, and heating the deposition cavity to enable the base material to be deposited to reach the deposition temperature;
and introducing a metal precursor into the deposition cavity through the first conduit, reacting the metal precursor with the surface of the substrate to be deposited, continuously introducing carrier gas, purging the residual metal precursor and reaction byproducts on the surface of the substrate to be deposited by utilizing the carrier gas, starting the discharge device, ionizing the carrier gas by the discharge device to generate plasma, continuously reacting the generated plasma with the surface of the substrate to be deposited, disconnecting the discharge device after reaction, purging the plasma and the reaction byproducts on the surface of the substrate to be deposited by utilizing the carrier gas, and repeating the steps to obtain the film layer by deposition on the surface of the substrate to be deposited.
Compared with the prior art, the plasma enhanced atomic layer deposition equipment and the deposition method have the following beneficial effects:
1. the plasma enhanced atomic layer deposition equipment comprises a first conduit and a second conduit, wherein the first conduit and the second conduit are utilized to separate a metal precursor from a carrier gas, on one hand, only the metal precursor (namely a metal source) passes through the first conduit, and due to self-limiting reaction of the metal source, a film layer cannot be further deposited, so that the aim of keeping a discharge area clean can be fulfilled; on the other hand, the sleeve design can protect the first conduit from being ignited and further protect the metal source from being ionized, because the electric field generated by the discharge device is greatly lost when passing through the deposition cavity, and once the carrier gas in the deposition cavity is ionized, the plasma is similar to fluid metal and can quickly offset the electric field, so that the electric field effect in the first conduit is further reduced, and no coating film remains; because the discharge area is in the deposition cavity, the carrier gases such as nitrogen, ammonia, oxygen, hydrogen, helium, argon and the like entering the deposition cavity are also gas barriers to prevent the metal precursor in the reaction area from flowing back; the plasma enhanced atomic layer deposition equipment can still keep the inner wall of a discharge area of a deposition cavity clean under the condition that a discharge device continuously discharges, so the equipment is also suitable for a PECVD process;
2. according to the plasma enhanced atomic layer deposition equipment, one end, close to the sample table, of the first guide pipe is communicated with the gas distributor, the metal precursor entering the first guide pipe enters the gas distributor and then reacts with the surface of the base material to be deposited through the vent holes, and the uniformity of the coating can be further improved through the gas distributor;
3. the plasma enhanced atomic layer deposition equipment also comprises a pre-loading cavity, and the deposition cavity and the pre-loading cavity are provided with independent vacuum pumping systems, so that the cavity is always in high vacuum in the coating process, the time of pumping from atmosphere to high vacuum in the traditional lofting process is saved, and the pollution to the coating cavity is reduced;
4. according to the plasma enhanced atomic layer deposition equipment, the end part of the first conduit, which is positioned outside the deposition cavity body, is provided with the plurality of inlets, the inlets are mutually independent, and each inlet is directly conveyed to the surface of the base material to be deposited, so that pollution is reduced, and the purity of a coated film is improved 。
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic structural diagram of a plasma enhanced atomic layer deposition apparatus according to an embodiment of the invention;
FIG. 2 is a schematic structural diagram of a plasma enhanced atomic layer deposition apparatus according to another embodiment of the invention;
FIG. 3 is a schematic structural diagram of a plasma enhanced atomic layer deposition apparatus according to another embodiment of the invention;
FIG. 4 is a schematic structural diagram of a plasma enhanced atomic layer deposition apparatus according to another embodiment of the invention;
fig. 5 is a schematic structural diagram of a plasma-enhanced atomic layer deposition apparatus according to another embodiment of the invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
An embodiment of the present application provides a plasma-enhanced atomic layer deposition apparatus, as shown in fig. 1 to 2, including:
the device comprises a deposition cavity 1, at least one sample stage 11 and a sample storage device, wherein the deposition cavity is internally provided with the sample stage;
the first guide pipe 2 is positioned in the deposition cavity 1, one end of the first guide pipe 2 is close to the sample table 11, and the other end of the first guide pipe extends upwards and penetrates out of the deposition cavity 1;
a second conduit 3 communicating with the deposition chamber 1;
and the discharge device is positioned outside the deposition cavity and is used for ionizing the carrier gas entering the deposition cavity through the second conduit.
It should be noted that the plasma enhanced atomic layer deposition apparatus of the present application includes a deposition cavity 1, a first conduit 2, a second conduit 3, and a discharge device, where a sample stage 11 is disposed in the deposition cavity 1, specifically, the number of the sample stages 11 may be determined according to an actual situation, for example, 2, 3, 4, 5 … … n, and the sample stage 11 is used to carry a substrate 10 to be deposited; when the device is applied, a carrier gas is introduced into the deposition cavity through the second conduit 3, and specifically, the carrier gas can be a reaction gas/inert gas such as nitrogen, ammonia, oxygen, hydrogen, helium, argon and the like; introducing a metal precursor into the reaction cavity through a first conduit 2; the electric field generated by the discharge device ionizes the carrier gas entering the deposition cavity through the second conduit to generate plasma; specifically, the discharge device is positioned outside the deposition cavity and above the sample stage 11, the second conduit 3 is positioned above the discharge device, and the area of the deposition cavity corresponding to the discharge device is called a discharge area; the metal precursor and the carrier gas are separated by the first conduit 2 and the second conduit 3, on one hand, only the metal precursor (namely the metal source) passes through the first conduit 2, and the film layer cannot be further deposited due to the self-limiting reaction of the metal source, so that the aim of keeping a discharge area clean can be fulfilled; on the other hand, the design of the sleeve can protect the first conduit 2 from fire striking, further protecting the metal source from ionization: since the electric field generated by the discharge device is largely lost while passing through the deposition chamber 1 and once the carrier gas in the deposition chamber 1 is ionized, the plasma is like a fluid metal, the electric field can be quickly offset, so that the electric field effect in the first conduit 2 is further reduced, and no coating film remains. Because the discharge region is arranged in the deposition cavity 1, the carrier gases such as nitrogen, ammonia, oxygen, hydrogen, helium, argon and the like entering the deposition cavity 1 are also gas barriers to prevent the metal precursor in the reaction region from flowing back and reacting. The equipment of the application can still keep the inner wall of the discharge area of the deposition cavity 1 clean under the condition that the discharge device continuously discharges, so the equipment is also suitable for the PECVD process.
In some embodiments, a heating device 4 is disposed on the deposition chamber 1 corresponding to the sample stage for heating the sample stage.
Specifically, a heating device 4 can be wrapped at a corresponding position outside the deposition cavity 1, the heating device is a conventional heating device, and the heating device 4 heats the sample stage to enable the base material to be deposited on the sample stage 11 to reach the deposition temperature; the area of the deposition cavity 1 corresponding to the sample stage 11 is called a reaction area. Specifically, the sample stage 11 can be arranged at the middle position of the deposition cavity 1, the corresponding heating device 4 is also arranged outside the middle position of the deposition cavity 1, and the heating device 4 only wraps the middle position of the deposition cavity 1, so that the heating temperature can reach thousands of degrees, the temperature range of coating is greatly increased, and the method can be applied to high-temperature modes such as MOCVD (metal organic chemical vapor deposition). Meanwhile, since the heating device 4 is located at the middle position of the deposition chamber 1, it can sufficiently heat the substrate 10 to be deposited and reduce the loss of the metal precursor.
Specifically, in some embodiments, a heating device is disposed on the deposition chamber corresponding to the sample stage, the heating device wraps the deposition chamber to heat the sample stage, and the sample stage may also be provided with a heating device to perform induction heating on the sample.
In some embodiments, a first vacuum system (not shown) is disposed outside the deposition chamber 1, and the first vacuum system is used for evacuating the deposition chamber 1. Specifically, the first vacuum-pumping system can be a vacuum pump, and the deposition cavity 1 can be vacuumized by using the vacuum pump; in practice, a vacuum adapter 12 may be disposed at the lower end of the deposition chamber 1, the vacuum adapter 12 is connected to a bellows 13, and the bellows is connected to the first vacuum-pumping system, so as to connect the first vacuum-pumping system to the deposition chamber 1.
In some embodiments, as shown in fig. 3 to 4, the deposition device further includes a pre-loading chamber 5, the pre-loading chamber 5 is communicated with the deposition chamber 1 through a gate valve 7, a pre-loading table 8 is disposed in the pre-loading chamber 5, the pre-loading table 8 is used for carrying a substrate to be deposited, and a mechanical conveying device 9 is further disposed in the pre-loading chamber 5 for conveying the substrate 10 to be deposited on the pre-loading table 8 to a sample table 11.
In the above embodiment, the mechanical transfer device 9 is an existing conventional transfer device, which can pick up the substrate 10 to be deposited on the pre-loading stage 8 and transfer it onto the sample stage 11. During the specific operation, firstly, under the atmospheric pressure environment, the substrate 10 to be deposited is placed on the pre-loading platform 8, then the pre-loading cavity 5 is pumped to a high vacuum state, then the gate valve 7 between the pre-loading cavity 5 and the deposition cavity 1 is opened, the sample platform 11 in the deposition cavity 1 of the pre-loading platform 8 is placed on the mechanical conveying device 9, and after the film coating is successful, the substrate to be deposited is conveyed back to the pre-loading platform 8 in the pre-loading cavity 5.
In some embodiments, the deposition support 50 and the pre-loading cavity 5 are further included, the deposition cavity 1 is installed on the deposition support 50, one end of the pre-loading cavity 5 is communicated with the deposition cavity 1, a joint of the pre-loading cavity 5 and the deposition cavity 50 is sealed by a sealing ring 54, the gate valve 7 is located in the pre-loading cavity 5, a blank breaking valve 51 is arranged above the gate valve 7 of the pre-loading cavity 5, a vacuum gauge 52 is arranged below the gate valve 7 of the pre-loading cavity 5, a second vacuum pumping system 53 is further arranged on the pre-loading cavity 5, a conveying rod 55 is arranged in the pre-loading cavity 5, a sample table is arranged on the top of the sample table, and the conveying rod 55 is used for conveying the sample table from the pre-loading cavity 5 to the deposition cavity 1.
Specifically, the second vacuum-pumping system may be a vacuum pump, and the pre-loading cavity 5 may be evacuated by using the vacuum pump; the pre-loading chamber 5 can be connected to the second evacuation system by means of a bellows, obviously, the deposition chamber 1 can also be connected to the first evacuation system by means of a bellows; this chamber has its own pumping and venting system and contains a sample carrier and a mechanical transfer device. Because the deposition cavity 1 and the pre-loading cavity 5 are provided with independent vacuum pumping systems, the cavities are always in high vacuum in the coating process, the time from atmosphere to high vacuum in the traditional lofting process is saved, and the pollution to the coating cavity is reduced.
Specifically, referring to fig. 5, the lower end of the deposition chamber 1 is in sealed communication with the pre-loading chamber 1 through a sealing ring 54; the deposition chamber 1 is mounted on the deposition bracket 50, specifically, a support member made of stainless steel and sealed by a rubber ring is additionally arranged at the upper part of the deposition chamber 1, so that the deposition chamber 1 is mounted; the pre-loading cavity 5 consists of two parts, wherein the upper part is used for bearing the lower part of the deposition cavity 1, the lower part is used for bearing the pre-loading cavity and is separated by a gate valve, and the two parts are respectively provided with a vacuum breaking valve and a vacuum gauge for respectively controlling and observing the vacuum degrees of the upper cavity and the lower cavity of the gate valve; a second vacuum-pumping system 53 and a quick-opening door 54 with a quartz window are also arranged on the pre-loading cavity 5, and are respectively used for vacuumizing and observing the condition inside the pre-loading cavity 5. In addition, there is a transfer rod 55, which has a length extending through the pre-load chamber and can reach the reaction zone of the deposition chamber 1; alternatively, the apparatus may be supported by welding portions of the quartz tube support and the stainless steel chamber to the deposition support 50. When in use, firstly, the pre-loading cavity 5 is ensured not to be in a vacuum condition, the gate valve 7 is closed, the conveying rod 55 is pulled out, and the height of the sample platform is approximately flush with the height of the quick-opening door 54; then the quick-opening door 54 is opened, a sample is placed on the sample platform, the quick-opening door 54 is closed to start pumping, after the sample is pumped to a certain vacuum condition, the gate valve 7 is opened to push the conveying rod 55, the height of the sample platform can be observed from the quartz tube at the upper end until the sample platform reaches the center of the wrapping area of the heating assembly, heating is started, the subsequent atomic layer deposition coating operation is started, the metal precursor and the plasma are alternately introduced according to the program setting, and then the carrier gas is utilized to purge. And after the coating is finished, closing the heating assembly, drawing out the conveying rod, closing the gate valve after the sample platform enters the vicinity of the quartz window on the quick-opening door and is ensured to leave the region of the gate valve, opening the air breaking valve of the pre-loading cavity, and opening the quick-opening door after air breaking to take out the coated sample. The advantages of the design of the above embodiment are: one pumping component is reduced, and the occupied area cost and the economic cost are saved; the problem of how to place the equipment is simply considered; the stainless steel cavity has stronger plasticity, and the cavity is easier to transform; similar to the design, other designs with the pre-loading cavity can also only arrange one pumping component in the pre-loading cavity, and the gate valve is not closed in the film coating process, so that the pre-loading cavity and the reaction cavity can be simultaneously ensured to be in a high vacuum state.
In some embodiments, the first conduit 2 and the second conduit 3 are provided with electromagnetic valves. The delivery of the gas source can be controlled by controlling the switch of the electromagnetic valve, and the first conduit 2 is directly communicated with the upper part of the substrate 10 to be deposited on the sample table 11, so that the effective contact between the metal precursor and the substrate 10 to be deposited is greatly increased.
In some embodiments, the sample stage 11 includes a sample holder 111 and a stage 112 disposed on the sample holder 111, wherein a side of the stage 112 is inclined, and an angle between the side of the stage 112 and a horizontal plane is 0-120 °.
In the above embodiment, the substrate 10 to be deposited is placed on the stage 112, and the shape of the stage is changed for the horizontal chamber, and the stage is arranged in a shape facing the gas inlet as much as possible because the plasma is very sensitive to the direction.
In some embodiments, the discharge device comprises an electrically conductive coil 14 wrapped outside the deposition chamber, or alternatively, the discharge device comprises parallel electrodes located outside the deposition chamber.
Specifically, the conductive coil 14 may be a copper coil, and an electric field generated by connecting two ends of the copper coil to the positive electrode and the negative electrode of the power supply respectively ionizes the carrier gas entering the deposition cavity through the second conduit to generate plasma; in practice, the conductive coil 14 is also connected to a controller that can adjust the switching of the electric field. The discharge device may employ parallel electrodes, using which plasma is generated, in addition to the conductive coil 14.
In some embodiments, the material used for the deposition chamber 1 corresponding to the position of the discharge device is quartz glass; the pre-loading cavity is made of stainless steel; in the above embodiment, the discharge region of the deposition chamber 1 is configured as a quartz tube for observing the ignition condition, and other parts far away from the discharge region can be made of stainless steel, including the chamber and part of the air inlet pipeline. In order to solve the problem that the height of the sample table cannot be observed, clamping grooves can be arranged at corresponding positions on the supporting rods, so that the sample table can be accurately placed to the required height without being observed through a quartz window.
In some embodiments, the pre-loading chamber 5 and the deposition chamber 1 are both arranged horizontally or vertically; the end of the first conduit 2 outside the deposition chamber 1 is provided with a plurality of inlets 21.
In the above embodiment, if the pre-loading chamber 5 and the deposition chamber 1 are vertically designed, the disadvantage is that the gas inlet is not uniform enough, and the gas flow distribution is not uniform due to the influence of gravity after the precursor enters the deposition chamber 1, and the advantage is that the sample stage is supported by the tube wall of the deposition chamber 1, and no additional load-bearing rod of the sample stage is required; the horizontal arrangement of the pre-loading cavity 5 and the deposition cavity 1 has the advantages that air inlet is uniform, and airflow distribution is more uniform after the precursor enters the deposition cavity 1; the end part of the first conduit 2, which is positioned outside the deposition cavity 1, is provided with a plurality of inlets 21, specifically, the inlets 21 are mutually independent, and each inlet 21 is directly conveyed to the surface of a substrate to be deposited, so that the pollution is reduced, and the purity of a coating film is improved.
In some embodiments, the diameter of the upper end of the deposition chamber 1 is smaller than the diameter of the middle and lower ends of the deposition chamber 1, the second guide tube 3 is located at one side of the upper end of the deposition chamber 1, and the discharge device is located at one side of the upper end of the deposition chamber 1 and below the second guide tube 3.
In some embodiments, one end of the first conduit 2 close to the sample stage is communicated with a gas distributor 6, the gas distributor 6 is hollow, and one end face of the gas distributor 6 far from the first conduit 2 is provided with a plurality of vent holes. Specifically, the shape of the gas distributor 6 can be cuboid, cube, round table shape and the like, the gas distributor 6 is hollow, a porous vent hole is formed in one end face close to the sample table 11, the metal precursor entering the first conduit 2 enters the gas distributor 6 and then reacts with the surface of the substrate 10 to be deposited through the vent hole, and the uniformity of the coating film can be further improved by arranging the gas distributor 6.
Based on the same inventive concept, the embodiment of the application also provides a plasma enhanced atomic layer deposition method, which comprises the following steps:
s1, providing the plasma enhanced atomic layer deposition equipment;
s2, placing the base material to be deposited on a sample table, vacuumizing a deposition cavity, introducing carrier gas into the deposition cavity through a second conduit, and heating the deposition cavity to enable the base material to be deposited to reach the deposition temperature;
s3, introducing a metal precursor into the deposition cavity through the first conduit, reacting the metal precursor with the surface of the substrate to be deposited, continuously introducing carrier gas, and purging the residual metal precursor and reaction byproducts on the surface of the substrate to be deposited by using the carrier gas; starting the discharge device, ionizing the carrier gas by the discharge device to generate plasma, continuously reacting the generated plasma with the surface of the base material to be deposited, disconnecting the discharge device after reaction, and purging the plasma and reaction byproducts on the surface of the base material to be deposited by using the carrier gas; the steps form a deposition period, and a film layer can be deposited on the surface of the base material to be deposited after the corresponding deposition period is repeatedly executed.
The following further describes a method for manufacturing a plasma enhanced atomic layer deposition apparatus according to the present application with specific examples. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified.
Example 1
The embodiment of the application provides a plasma enhanced atomic layer deposition method, which comprises the following steps:
s1, providing the plasma enhanced atomic layer deposition equipment;
s2, placing the silicon wafer to be deposited on a sample table, vacuumizing a deposition cavity until the pressure is about 5Pa, introducing oxygen serving as carrier gas into the deposition cavity through a second conduit, heating the deposition cavity to keep the temperature of the substrate to be deposited at 300 ℃, and starting to perform thin film deposition after 30 minutes;
s3, introducing a metal precursor trimethylaluminum into the deposition cavity through the first conduit, and reacting the trimethylaluminum with the surface of the silicon wafer to generate Al(CH 3 ) x The injection time is 14ms; then, introducing oxygen into the deposition cavity through a second conduit, and purging the residual trimethylaluminum and reaction byproducts on the surface of the silicon wafer by using the oxygen, wherein the oxygen injection time is 2min; after the conductive coil is connected with a power supply, oxygen is ionized to obtain ozone, the ozone has strong oxidizing capacity, and Al (CH) on the surface of the silicon wafer is oxidized 3 ) x Oxidation to form AlO x The film is coated on the surface of the silicon wafer, the ionization time is 2min, and finally 2min of oxygen is injected to purge the reaction by-products which can not completely react with ozone, the steps are required by vapor deposition in one period, and the silicon wafer coated with the alumina film layer successfully is obtained after 50 periods of total growth.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A plasma-enhanced atomic layer deposition apparatus, comprising:
the deposition cavity is internally provided with a sample table;
the first guide pipe is positioned in the deposition cavity, one end of the first guide pipe is close to the sample table, and the other end of the first guide pipe extends upwards and penetrates out of the deposition cavity;
a second conduit in communication with the deposition chamber;
and the discharge device is positioned outside the deposition cavity and is used for ionizing the carrier gas entering the deposition cavity through the second conduit.
2. The apparatus according to claim 1, wherein the deposition chamber is provided with a heating device corresponding to the sample stage for heating the sample stage.
3. The apparatus according to claim 1, wherein a first vacuum system is disposed outside the deposition chamber, and the first vacuum system is configured to evacuate the deposition chamber.
4. The apparatus according to claim 1, further comprising a pre-loading chamber, wherein the pre-loading chamber is communicated with the deposition chamber through a gate valve, a pre-loading table is arranged in the pre-loading chamber, the pre-loading table is used for carrying a substrate to be deposited, and a mechanical conveying device is further arranged in the pre-loading chamber and used for conveying the substrate to be deposited on the pre-loading table to the sample table.
5. The plasma-enhanced atomic layer deposition device according to claim 1, further comprising a deposition support and a pre-loading cavity, wherein the deposition cavity is mounted on the deposition support, one end of the pre-loading cavity is communicated with the deposition cavity, a joint of the pre-loading cavity and the deposition cavity is sealed by a sealing ring, a gate valve is located in the pre-loading cavity, a blank breaking valve is arranged above the gate valve in the pre-loading cavity, a vacuum gauge is arranged below the gate valve in the pre-loading cavity, a second vacuum pumping system and a quick opening door are further arranged on the pre-loading cavity, a conveying rod is arranged in the pre-loading cavity, a sample table is arranged at the top of the conveying rod, and the conveying rod is used for conveying the sample table from the pre-loading cavity to the deposition cavity.
6. The apparatus according to claim 1, wherein the first conduit and the second conduit are each provided with a solenoid valve;
the sample stage comprises a sample support and an object stage arranged on the sample support, wherein one side of the object stage is obliquely arranged, and an included angle between one side of the object stage and the horizontal plane is 0-120 degrees.
7. The plasma-enhanced atomic layer deposition apparatus of claim 1, wherein the discharge device comprises a conductive coil wrapped outside the deposition chamber;
or, the discharge device comprises parallel electrodes positioned outside the deposition cavity.
8. The apparatus according to claim 4 or 5, wherein the pre-loading chamber and the deposition chamber are both horizontally or vertically arranged;
the deposition cavity body is made of quartz glass corresponding to the position of the discharge device;
the pre-loading cavity is made of stainless steel;
the end of the first conduit outside the deposition cavity is provided with a plurality of inlets.
9. The apparatus according to claim 1, wherein a gas distributor is connected to an end of the first conduit close to the sample stage, the gas distributor is hollow, and a plurality of vent holes are formed in an end surface of the gas distributor far from the first conduit.
10. A method of plasma enhanced atomic layer deposition comprising the steps of:
providing a plasma enhanced atomic layer deposition apparatus as claimed in any one of claims 1 to 9;
placing the base material to be deposited on a sample table, vacuumizing a deposition cavity, introducing carrier gas into the deposition cavity through a second conduit, and heating the deposition cavity to enable the base material to be deposited to reach the deposition temperature;
and introducing a metal precursor into the deposition cavity through the first conduit, reacting the metal precursor with the surface of the substrate to be deposited, continuously introducing carrier gas, purging the residual metal precursor and reaction byproducts on the surface of the substrate to be deposited by utilizing the carrier gas, starting the discharge device, ionizing the carrier gas by the discharge device to generate plasma, continuously reacting the generated plasma with the surface of the substrate to be deposited, disconnecting the discharge device after reaction, purging the plasma and the reaction byproducts on the surface of the substrate to be deposited by utilizing the carrier gas, and repeating the steps to obtain the film layer by deposition on the surface of the substrate to be deposited.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0183254A2 (en) * | 1984-11-29 | 1986-06-04 | Matsushita Electric Industrial Co., Ltd. | Plasma CVD apparatus and method for forming a diamond-like carbon film |
| US5180435A (en) * | 1987-09-24 | 1993-01-19 | Research Triangle Institute, Inc. | Remote plasma enhanced CVD method and apparatus for growing an epitaxial semiconductor layer |
| CN101041893A (en) * | 2006-03-21 | 2007-09-26 | 韩商奥拓股份有限公司 | Apparatus for depositing atomic layer using gas separation type showerhead |
| CN101969020A (en) * | 2009-07-27 | 2011-02-09 | 奥拓股份有限公司 | Deposition apparatus and method of manufacturing a semiconductor device |
| CN102892922A (en) * | 2010-03-17 | 2013-01-23 | 应用材料公司 | Method and apparatus for remote plasma source assisted silicon-containing film deposition |
| CN203174200U (en) * | 2013-04-03 | 2013-09-04 | 王东君 | Plasma enhanced atomic layer deposition equipment |
| CN108149224A (en) * | 2018-01-08 | 2018-06-12 | 上海硕余精密机械设备有限公司 | A kind of plasma-assisted atomic layer deposition apparatus |
| CN110396675A (en) * | 2019-07-10 | 2019-11-01 | 中国科学院电工研究所 | A kind of preparation method of plasma enhanced chemical vapor deposition metallic film |
-
2022
- 2022-10-31 CN CN202211346014.XA patent/CN115595561A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0183254A2 (en) * | 1984-11-29 | 1986-06-04 | Matsushita Electric Industrial Co., Ltd. | Plasma CVD apparatus and method for forming a diamond-like carbon film |
| US5180435A (en) * | 1987-09-24 | 1993-01-19 | Research Triangle Institute, Inc. | Remote plasma enhanced CVD method and apparatus for growing an epitaxial semiconductor layer |
| CN101041893A (en) * | 2006-03-21 | 2007-09-26 | 韩商奥拓股份有限公司 | Apparatus for depositing atomic layer using gas separation type showerhead |
| CN101969020A (en) * | 2009-07-27 | 2011-02-09 | 奥拓股份有限公司 | Deposition apparatus and method of manufacturing a semiconductor device |
| CN102892922A (en) * | 2010-03-17 | 2013-01-23 | 应用材料公司 | Method and apparatus for remote plasma source assisted silicon-containing film deposition |
| CN203174200U (en) * | 2013-04-03 | 2013-09-04 | 王东君 | Plasma enhanced atomic layer deposition equipment |
| CN108149224A (en) * | 2018-01-08 | 2018-06-12 | 上海硕余精密机械设备有限公司 | A kind of plasma-assisted atomic layer deposition apparatus |
| CN110396675A (en) * | 2019-07-10 | 2019-11-01 | 中国科学院电工研究所 | A kind of preparation method of plasma enhanced chemical vapor deposition metallic film |
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