KR20160137743A - Atomic layer deposition apparatus and methods - Google Patents

Atomic layer deposition apparatus and methods Download PDF

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Publication number
KR20160137743A
KR20160137743A KR1020150070564A KR20150070564A KR20160137743A KR 20160137743 A KR20160137743 A KR 20160137743A KR 1020150070564 A KR1020150070564 A KR 1020150070564A KR 20150070564 A KR20150070564 A KR 20150070564A KR 20160137743 A KR20160137743 A KR 20160137743A
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KR
South Korea
Prior art keywords
substrate
oxygen gas
oxygen
precursor
reaction layer
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KR1020150070564A
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Korean (ko)
Inventor
정인권
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주식회사 엠티에스나노테크
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Priority to KR1020150070564A priority Critical patent/KR20160137743A/en
Publication of KR20160137743A publication Critical patent/KR20160137743A/en

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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]
    • 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]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/45538—Plasma being used continuously during the ALD cycle
    • 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
    • C23C16/45563—Gas nozzles
    • C23C16/45565—Shower nozzles

Abstract

The present invention deposits only the first reaction layer on the substrate while moving the substrate along the first direction and deposits only the second reaction layer on the substrate while moving the substrate in the opposite direction of the first direction. During the movement in the first direction, the raw precursor is injected onto the substrate through the precursor injection channel to deposit a first reaction layer on the substrate surface, oxygen gas is injected through the oxygen gas injection channel onto the first reaction layer Spray and purge. During at least a portion of the movement in the opposite direction of the first direction, an oxygen plasma is injected onto the substrate through the oxygen gas injection channel to deposit the second reaction layer on the first reaction layer.

Description

[0001] ATOMIC LAYER DEPOSITION APPARATUS AND METHODS [0002]

The present invention relates to a thin film deposition apparatus, and more particularly, to an atomic layer deposition apparatus and method for depositing an atomic layer on a substrate.

Atomic layer deposition is widely used as a method of depositing a thin film on a semiconductor wafer, and is being applied to a method of depositing a thin film on a CIGS solar cell substrate, a Si solar cell substrate, and an OLED display substrate. A typical atomic layer deposition process consists of four steps as follows:

In the first step, a source precursor, for example TMA (trimethyl-aluminum), is injected onto the substrate. The raw precursor reacts with the surface of the substrate to coat the substrate surface with the first reaction layer.

In the purge gas injection step, which is the second step, an inert gas such as nitrogen is injected onto the substrate to remove the raw material precursor that is physically adsorbed on the substrate surface.

In a third step, a reactant precursor, for example H 2 O, is injected onto the substrate. The reaction precursor reacts with the first reaction layer to coat the substrate surface with the second reaction layer.

In the fourth purge gas injection step, an inert gas is injected onto the substrate to remove the reaction precursor physically adsorbed on the substrate surface. By this cycle, a single layer of a first reaction layer and a second reaction layer, for example, an Al 2 O 3 thin film, is deposited on the substrate. The cycle is repeated to obtain a thin film having a desired thickness.

The thin film deposition rate by the atomic layer deposition method is determined by the time required for the cycle consisting of the above four steps. Since the raw precursor, the purge gas, the reaction precursor and the purge gas are sequentially supplied, the deposition rate is slow have.

1 and 2, a space division method which is another atomic layer deposition method will be described. 1 and 2 are a side view and a plan view of an atomic layer deposition apparatus by a space division method, respectively. As shown in FIG. 1, in the space division system, a reaction precursor ejection port 21, an exhaust port 22, a purge gas ejection port 23, an exhaust port 24, a precursor ejection port 25, an exhaust port 26, And a showerhead 20 constituted of a reaction chamber 27, an exhaust port 28 and a reaction precursor ejection port 29. A second reaction layer is formed on the substrate 50 by passing the substrate 50 under the showerhead, 1 reaction layer and the second reaction layer are sequentially coated. The advantage of this method is that the productivity is high as compared with the atomic layer deposition method comprising the above four steps since the raw material precursor, the reaction precursor and the purge gas are simultaneously injected onto the substrate 50.

However, in this method, in order to obtain a uniform film thickness at the edge 50a and the central portion 50b of the substrate, the substrate 50 must be completely penetrated under the shower head 20 as shown in FIG. 2, There is a problem in that the moving distance of the motor becomes longer and the size of the motor becomes larger.

In addition, in order to deposit a thin film having a desired thickness at a high speed, there is a problem that the substrate must be reciprocally moved 52 at a high speed by a distance corresponding to the width of the shower head 50w plus the width 20w of the showerhead. This problem becomes more pronounced as the width 50w of the substrate or the width 20w of the shower head becomes larger. For example, a CIGS solar cell substrate has a width of 1200 mm and a length of 600 mm, so the minimum moving distance of the substrate is 600 mm or more. Another example is a 5.5G OLED display substrate with a width of 1500mm and a height of 1300mm, so the minimum moving distance of the substrate is more than 1300mm.

In addition, since the gas is simultaneously injected toward the substrate, the precursor of the material is diffused and mixed with each other, so that particles are generated by direct reaction between the precursors. To prevent such diffusion, it is important to keep the distance between the substrate and the showerhead 20 to a minimum. However, it is not easy to keep the gap to a minimum in consideration of the size and movement distance of the substrate 50.

As described above, in the atomic layer deposition, there is a need for an atomic layer deposition apparatus and a method which are designed so that the raw material precursor and the reaction precursor are not mixed with each other while reducing the cycle time.

It is an object of the present invention to provide an apparatus and a method for depositing an atomic layer in which a raw material precursor and a reaction precursor are not mixed with each other and a cycle time is reduced.

The present invention deposits only the first reaction layer on the substrate while moving the substrate along the first direction and deposits only the second reaction layer on the substrate while moving the substrate in the opposite direction of the first direction.

During at least a portion of the movement in the first direction, the source precursor is injected onto the substrate through the precursor precursor injection channel to deposit the first reaction layer on at least a portion of the substrate surface. Also, oxygen gas is injected onto the substrate through the oxygen gas injection channel during at least part of the movement in the first direction. Oxygen gas is used to purge the raw material precursor and reaction by-products that remain adsorbed on the first reaction layer.

During at least a part of the movement in the opposite direction of the first direction, oxygen gas is supplied through the oxygen gas injection channel while plasma power is applied to the oxygen gas to convert it into oxygen plasma, and the oxygen plasma is injected onto the substrate, 2 Reaction layer is deposited. And oxygen gas is injected onto the substrate through the oxygen gas injection channel in an ecology where no plasma power is applied during at least a part of the movement in the reverse direction of the first direction. The oxygen gas is adsorbed on the second reaction layer to purge the remaining oxygen plasma and reaction by-products.

According to the present invention, it is possible to secure an atomic layer deposition apparatus and a method capable of reducing the cycle time and preventing generation of particles due to the premix of the raw material precursor and the reaction precursor.

1 is a side view of an atomic layer deposition apparatus according to the prior art;
2 is a plan view of an atomic layer deposition apparatus according to the prior art;
3 to 11 are sectional views of an atomic layer deposition apparatus according to an embodiment of the present invention.

3 is a cross-sectional view of an atomic layer deposition apparatus 200 according to an embodiment of the present invention. The atomic layer deposition apparatus 200 includes a reaction chamber 100 and a showerhead 110. Inside the reaction chamber 100, a substrate support 55 capable of reciprocating motion is provided.

The showerhead 110 includes at least one raw precursor injection channel 10, a first oxygen gas injection channel 20, a second oxygen gas injection channel 22, a raw precursor injection channel 10, A first exhaust channel 30 disposed between the gas injection channels 20 and a second exhaust channel 32 disposed between the precursor precursor injection channel 10 and the second oxygen gas injection channel 22 . The raw precursor 14 is injected into the chamber 100 to be injected toward the substrate 50 through the precursor injecting channel 10 and the injected precursor 14 is injected into the first and second exhaust channels 30 and 32 . The oxygen gas 24 is injected into the chamber 100 to be injected toward the substrate 50 through the oxygen gas injection channels 30 and 32 and is injected into the chamber 100 through the exhaust channels 30 and 32, And exhausted to the outside.

According to one embodiment, the first exhaust channel 30 includes a third exhaust channel disposed closer to the first oxygen gas injection channel 30 and a third exhaust channel disposed further adjacent to the raw precursor injection channel 10, And in this embodiment the oxygen gas 24 is mainly exhausted through the third exhaust channel and the raw precursor 14 is mainly exhausted through the fourth exhaust channel.

According to one embodiment, the second exhaust channel 32 includes a fifth exhaust channel disposed closer to the second oxygen gas injection channel 32 and a sixth exhaust channel disposed further adjacent the raw precursor injection channel 10, The oxygen gas 24 is mainly exhausted through the fifth exhaust channel, and the raw precursor 14 is mainly exhausted through the sixth exhaust channel.

A conductive electrode rod (25) is disposed in the oxygen gas injection channel (20). Plasma power can be applied to the conductive electrode 25. As a source of the plasma power, an RF alternating current or a pulse direct current can be used. When plasma power is applied to the conductive electrode 25, oxygen gas injected through the oxygen injection channel 20 is converted into oxygen plasma while passing around the conductive electrode 25. The oxygen plasma may include oxygen radicals, oxygen ions, electrons, and the like.

An oxygen plasma 26 is generated and supplied onto the substrate when plasma power is applied while oxygen gas 24 is injected through the oxygen gas channels 30 and 32. When plasma power is not applied, Can be supplied onto the substrate in the form of a film. The oxygen plasma 26 is used as the reaction precursor 16 and the oxygen gas 24 can be used as the purge gas when the oxygen gas 24 does not react with the precursor 13.

The substrate support 55 is mounted within the chamber 100 and configured to support the substrate 50 and includes a substrate precursor injection channel 10, oxygen gas injection channels 20 and 22, 30 and 32, respectively. The substrate support 55 is also configured to reciprocate the substrate 50 along the first direction 60. The first direction 60 is the direction in which the substrate 50 can be moved across the gas injection channels 10, 20 and 22 and the exhaust channels 30 and 32.

Referring to Figs. 4 to 11, an embodiment of a method of depositing an aluminum oxide film using the atomic layer deposition apparatus 100 includes the following steps. 4 to 11 are cross-sectional views of the atomic layer deposition apparatus 200. TMA (trimethylaluminum) may be used as the raw precursor containing aluminum. As the reaction precursor containing oxygen, an oxygen plasma can be used.

(1) As shown in FIG. 4, any point 52 on the substrate 50 is introduced into the first oxygen gas injection channel 20 (see FIG. 4) while the TMA 14 and the oxygen gas 24 are injected into the chamber 200, ) Substrate placement and gas injection step 300,

(2) The substrate 50 is moved along the first direction 60 from FIG. 4 to FIG. 5 so that the arbitrary point 52 is exposed to the oxygen gas 24 near the first oxygen gas injection channel 20 A first shifting phase and first purge step 310 for shifting to the same state,

(3) the substrate 50 is exposed to the TMA gas 14 in the vicinity of the TMA implantation channel 10 to deposit an aluminum atomic layer, which is the first reaction layer, on the point 52, A second movement step and a first reaction layer formation step (320) for moving the substrate along the direction (60) from the state shown in FIG. 5 to the state shown in FIG. 6,

6 to 7 in the first direction 60 so that the oxygen gas 24 is exposed and purged at any point 52 near the second oxygen gas injection channel 22. [ A third shifting step and a second purge step 330 for shifting to the first shifting state,

(5) As shown in FIG. 8, the injection precursor injection blocking step (340) for blocking injection of the TMA (14)

(7) a fifth movement step 350 of applying plasma power to the electrode rods 25 to generate the oxygen plasma 26 and moving the substrate 55 in a direction opposite to the first direction 60, as shown in FIG. 9; ,

(8) An optional point 52 is exposed to the oxygen plasma 26 near at least one of the first and second oxygen gas injection channels 20 and 22 to form an oxygen layer And a sixth transfer step and a second reaction layer deposition step (360) for moving the substrate (50) in the reverse direction of the first direction (60) to the state shown in FIG.

After the second reactive layer deposition step 360 is completed, the process returns to the substrate placement and gas injection step 300 and repeats the steps sequentially to form an aluminum layer as the first reaction layer and an oxygen layer as the second reaction layer, 50 on an arbitrary point 52 on the substrate.

According to one embodiment, instead of injecting the TMA 14 in the substrate placement and gas injection step 300, it is also possible to inject the TMA 14 gas after the first movement step 310 is completed.

According to one embodiment, it is also possible to block the injection of the TMA 14 gas before the third movement step 330 is started after the second movement step 320 is finished.

According to one embodiment, inert gas may be injected into the chamber 100 through the precursor precursor injection channel 10 during the time that the TMA 14 is not injected through the precursor precursor injection channel 10 to be used as a purge gas . Argon, nitrogen and oxygen, which are inert gases, may be used.

According to one embodiment, the oxygen plasma 26 may be generated by applying a plasma power to the electrode 25 while injecting the oxygen gas 24, And may be provided on the substrate through the oxygen gas injection channel 24. In this embodiment, the showerhead 110 does not need to have the electrode bar 25.

It is also possible to deposit another metal oxide instead of the aluminum oxide film by an atomic layer deposition method by using a raw material precursor containing another metal element instead of TMA. Also, in the case of depositing a metal nitride instead of a metal oxide, a gas containing a nitrogen component may be injected instead of oxygen gas, and plasma power may be applied to the conductive electrode 25 to generate a nitrogen plasma to be used as a reaction precursor.

While the invention has been described with reference to specific embodiments, the invention is not to be limited by the specific embodiments described, but may be advantageously applied to modified embodiments which are within the scope of the invention.

10 raw precursor injection channel 14 raw precursor
20 and 22 Oxygen gas injection channel 24 Oxygen gas
26 Oxygen plasma 30 and 32 exhaust channels
50 substrate 55 substrate support
100 chamber 200 atomic layer deposition apparatus

Claims (3)

At least one source precursor implantation channel, at least one oxygen gas and an oxygen plasma implantation channel, an electrode for plasma application disposed in the oxygen gas and oxygen plasma implantation channel, at least one of the source precursor and at least one Preparing a reaction chamber having a showerhead including an exhaust channel of the reaction chamber and a substrate support configured to be reciprocatable;
A substrate mounting step of mounting a substrate on the substrate support;
A substrate positioning step of moving the substrate support to position the substrate adjacent to the showerhead;
An oxygen gas injection step of injecting and discharging oxygen gas toward the substrate through the oxygen gas and the oxygen plasma injection channel;
A first moving step of moving the substrate along a first direction;
A first reaction layer formation that forms a first reaction layer on at least a portion of the substrate by injecting and exhausting the source precursor onto the substrate through the source precursor injection channel toward the substrate during at least a portion of the first movement step step;
A first purge step of exposing the first reaction layer to the oxygen gas during at least a part of the first movement step to purge the surface of the first reaction layer by the oxygen gas;
Stopping the supply of the precursor of the raw material to stop the injection of the precursor;
A second moving step of moving the substrate in a direction opposite to the first direction; And
Forming a second reaction layer forming an oxygen-containing second reaction layer on the first reaction layer by injecting and exhausting an oxygen plasma onto the substrate through the oxygen gas injection channel during at least a portion of the second movement step And depositing an atomic layer on the substrate. The method according to claim 1,
Wherein the oxygen plasma is generated by applying plasma power to the oxygen gas while the oxygen gas is injected through the oxygen gas injection channel. The method according to claim 1,
Wherein the oxygen plasma is generated in a remote plasma generator installed outside the showerhead and supplied onto the substrate through the showerhead.
KR1020150070564A 2015-05-20 2015-05-20 Atomic layer deposition apparatus and methods KR20160137743A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107201509A (en) * 2017-05-17 2017-09-26 李哲峰 A kind of apparatus for atomic layer deposition and method with same plasma source
KR20190086236A (en) 2018-01-12 2019-07-22 (주)리드 Apparatus for atomic layer deposition
KR20200077655A (en) 2018-12-20 2020-07-01 (주)리드 Apparatus for atomic layer deposition
WO2021120541A1 (en) * 2019-12-18 2021-06-24 江苏菲沃泰纳米科技有限公司 Coating device and coating method therefor
CN113737156A (en) * 2021-07-19 2021-12-03 华中科技大学 Atomic layer deposition apparatus and method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107201509A (en) * 2017-05-17 2017-09-26 李哲峰 A kind of apparatus for atomic layer deposition and method with same plasma source
KR20190086236A (en) 2018-01-12 2019-07-22 (주)리드 Apparatus for atomic layer deposition
KR20200077655A (en) 2018-12-20 2020-07-01 (주)리드 Apparatus for atomic layer deposition
WO2021120541A1 (en) * 2019-12-18 2021-06-24 江苏菲沃泰纳米科技有限公司 Coating device and coating method therefor
US11898248B2 (en) 2019-12-18 2024-02-13 Jiangsu Favored Nanotechnology Co., Ltd. Coating apparatus and coating method
CN113737156A (en) * 2021-07-19 2021-12-03 华中科技大学 Atomic layer deposition apparatus and method
WO2023000372A1 (en) * 2021-07-19 2023-01-26 华中科技大学 Atomic layer deposition device and method

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