JP2020111767A - Atomic layer deposition apparatus and film deposition method - Google Patents

Abstract

To provide an atomic layer deposition apparatus and a film deposition method, capable of controlling displacement of each reaction chamber, forming a suitable atomic layer and preventing a reactant from being deposited in the inside of an apparatus to suppress contamination in the apparatus.SOLUTION: An atomic layer deposition apparatus 1 includes an exhaust pipe 23 connected between each of a plurality of reaction chambers 20 and an exhaust pump and capable of controlling displacement. At least one of a first supply pipe 21 and a second supply pipe 22 is connected to each of the plurality of reaction chambers 20, and exhaust is performed by the exhaust pipe 23 from each of the plurality of reaction chambers 20 supplied with gas including a first precursor or a second precursor.SELECTED DRAWING: Figure 1

Description

The present invention relates to an atomic layer deposition apparatus and a film forming method using an atomic layer deposition method.

Atomic Layer Deposition (hereinafter, referred to as “ALD”) is a method for forming a dense thin film without pinholes along a surface shape of a base material by using a semiconductor high dielectric constant material (High-k). And is used for insulation layers.
Here, the basic flow of ALD will be described. In the first step, the gaseous first precursor is supplied to the base material that is left standing in the reaction vessel, and the first precursor is saturated and adsorbed (chemisorption) on the base material. In the subsequent second step, a purge gas is introduced into the reaction vessel to remove the excess first precursor (physically adsorbed) on the surface of the base material. In the subsequent third step, a gaseous second precursor is introduced into the reaction vessel, and the first and second precursors saturated and adsorbed on the surface are reacted to form a desired substance that forms an atomic layer. Let In the subsequent fourth step, the purge gas is again introduced into the reaction vessel to remove the excess second precursor on the surface of the base material. Usually, these four steps constitute one cycle, which is the basic unit of ALD. In ALD, the above cycle is repeated a desired number of times depending on the thickness of the thin film to be formed and the like.
The above-mentioned ALD for switching the gas in the reaction container is also called a time-division ALD (Temporal ALD, hereinafter sometimes referred to as “TALD”). In each step of ALD, appropriate exposure conditions (precursor partial pressure, exposure time, substrate temperature, etc.) are determined by the material of the substrate, the composition of the precursor, and their reactivity. In the TALD, the vapor pressure of the precursor gas is controlled by adjusting the temperature of the precursor container in which the precursor gas to be supplied to the reaction container is housed and the pipe connecting the precursor container and the reaction container. The flow rate of the precursor gas is controlled using a mass flow meter or the like, and the exposure time is controlled using a high speed valve that opens and closes a pipe for supplying gas to the reaction container. In TALD, a high quality thin film without pinholes can be formed by adjusting the exposure condition to an appropriate range.
On the other hand, in TALD, although a high quality thin film can be formed, one cycle usually requires several tens of seconds to several minutes, and there is room for improvement in processing capacity (throughput).
Regarding the improvement of the processing capacity, a space-division ALD (Spatial ALD, which may be hereinafter referred to as “SALD”) in which each step is performed while sequentially moving a substrate to a space of a different gas atmosphere has been attracting attention in recent years. ..
In SALD, the first step is performed by allowing the base material to stay in the gas atmosphere space of the first precursor for a predetermined time. Next, the base material is moved to an atmosphere space of purge gas to perform the second step. Further, when the substrate is moved to the gas atmosphere space of the second precursor and the third step is performed, and finally the substrate is moved to the atmosphere space of the purge gas and the fourth step is performed, the above-mentioned one cycle is completed. ..
In SALD, since a plurality of base materials can be arranged in each of the above-mentioned spaces, ALD of a plurality of base materials can be performed in parallel, and as a result, improvement in processing capacity can be expected.

Japanese Patent No. 4532157 Japanese Patent No. 5778174

However, in the film forming method of Patent Document 1, since the entire chamber is exhausted from one exhaust port, the precursor gas introduced into each station is released into the chamber. For this reason, the source gas and the oxidizing gas may react in the chamber, and an oxide may be deposited at an unintended portion to cause contamination with the reactant. Further, there is a problem that the reaction process of atomic layer deposition on the substrate is not established.
Further, in the film forming method described in Patent Document 2, the oxidizing gas injected into the oxidation zone is exhausted from the precursor chamber into which the first precursor gas is introduced. In this method, the precursor does not flow into the oxidation zone, but the oxidizing gas activated by plasma or the like enters the precursor zone, and the oxide is deposited at an unintended location, thus contaminating the reactant. May occur. In addition, the reaction process of atomic layer deposition on the substrate may not be established.
At this time, a purge zone or the like may be provided between the oxidation zone and the zone for introducing the precursor (precursor zone) to provide a space. However, in this case, the size of the apparatus becomes large, which is not preferable. In addition, as the size of the apparatus becomes larger, the transport path of the base material becomes longer, which lowers the productivity.
Therefore, it is an object of the present invention to provide an atomic layer deposition apparatus and a film forming method capable of adjusting the exhaust amount of each reaction chamber, forming a suitable atomic layer, and suppressing contamination in the apparatus.

A first aspect of the present invention is an atomic layer deposition apparatus for forming an atomic layer on a flexible base material by using an atomic layer deposition method, the unwinding chamber in which the flexible base material is unwound, and the atomic layer. A winding chamber in which the flexible substrate on which the flexible substrate is wound is wound, and a plurality of reaction chambers in which the flexible substrate is allowed to pass between the unwinding chamber and the winding chamber, A first supply unit containing a precursor-containing gas, a first supply pipe connected to the first supply unit, a second supply unit containing a second precursor-containing gas, and the second A second supply pipe connected to a supply unit, an exhaust pipe connected to each of the plurality of reaction chambers and a pump for exhaust gas and capable of adjusting the exhaust amount, and each of the plurality of reaction chambers Is connected to at least one of the first supply pipe and the second supply pipe, and from each of the plurality of reaction chambers to which a gas containing the first precursor or the second precursor is supplied. It is characterized in that exhaust is performed by the exhaust pipe.

Another aspect of the present invention is an atomic layer deposition apparatus for forming an atomic layer on a flexible substrate using an atomic layer deposition method, wherein an unwinding chamber in which the flexible substrate is unwound and the atomic layer are A winding chamber in which the formed flexible substrate is wound, a plurality of reaction chambers in which the flexible substrate is allowed to pass between the unwinding chamber and the winding chamber, and a first precursor A first supply unit containing a gas containing a body, a first supply pipe connected to the first supply unit, a second supply unit containing a gas containing a second precursor, and the second supply Supply pipe connected to the section, a third supply unit containing a gas containing a third precursor, a third supply pipe connected to the third supply unit, and each of the plurality of reaction chambers And an exhaust pipe that is connected to an exhaust pump and whose exhaust amount can be adjusted, and each of the plurality of reaction chambers includes the first supply pipe, the second supply pipe, and the third supply pipe. At least one of them is connected, and gas is exhausted from the reaction chamber supplied with the gas containing the precursor through the exhaust pipe.
Yet another aspect of the present invention is a film forming method for forming an atomic layer on a flexible substrate by a space division atomic layer deposition method, wherein the flexible substrate is provided so as to pass therethrough, and a first precursor , A plurality of reaction chambers supplied with a gas containing a second precursor, the atomic layer is formed by passing the flexible substrate, the gas containing the first precursor or the second precursor Emission is performed by an exhaust pipe connected to the plurality of reaction chambers to which the gas containing the gas is supplied and the exhaust pump.

According to the atomic layer deposition apparatus and the film forming method of the present invention, it is possible to adjust the exhaust amount of each reaction chamber, form a suitable atomic layer, suppress the deposition of reactants inside the apparatus, and contaminate the inside of the apparatus. It is possible to provide an atomic layer deposition apparatus and a film forming method capable of suppressing the above.

It is a schematic diagram which shows the internal structure of the atomic layer deposition apparatus which concerns on 1st embodiment of this invention. It is a schematic diagram which shows the internal structure which looked at the atomic layer deposition apparatus which concerns on 1st embodiment of this invention from the direction different from FIG. It is a schematic diagram which shows the internal structure of the atomic layer deposition apparatus which concerns on 2nd embodiment of this invention.

[First embodiment]
A first embodiment of the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is a schematic diagram of an internal structure of a top view of an atomic layer deposition apparatus 1 according to a first embodiment of the present invention. 2 is a schematic diagram of the internal structure of the atomic layer deposition apparatus 2 as viewed from the side.

The atomic layer deposition apparatus 1 is an apparatus that forms a thin film by depositing an atomic layer by SALD on the surface of the flexible substrate 3 by roll-to-roll (roll to roll).
The atomic layer deposition apparatus 1 includes a plurality of reaction chambers 20 arranged between an unwinding chamber 10 to which the flexible substrate 3 is sent out and a winding chamber 30. In FIG. 1, eight reaction chambers 20 (reaction chambers 20A to 20H) are shown as an example. Hereinafter, the reaction chambers 20A to 20H may be collectively referred to as the reaction chamber 20.

The unwinding chamber 10 includes an unwinding roll 11. The flexible base material 3, which is a target for forming an atomic layer, is wound around the unwinding roll 11 in a roll shape. When the unwinding roll 11 is rotated, the flexible base material 3 is sequentially sent out to each reaction chamber 20.
The winding chamber 30 includes a winding roll 31. When the take-up roll 31 is rotated, the flexible substrate 3 that has come out of the reaction chamber 20 (reaction chamber 20H in this example) immediately before the take-up chamber 30 is taken up by the take-up roll 31.

As shown in FIG. 1, two supply pipes, a first supply pipe 21 and a second supply pipe 22, are connected to the reaction chambers 20A to 20H, respectively.
The first supply pipes 21 connected to the reaction chambers 20 join together on the upstream side and are connected to the first supply unit 27. The first supply unit 27 contains a gas containing a first precursor (hereinafter, may be referred to as “first precursor gas”).
Further, the second supply pipes 22 connected to the reaction chambers 20 join together on the upstream side and are connected to the second supply unit 28. The second supply unit 28 contains a gas containing a second precursor (hereinafter, may be referred to as “second precursor gas”).
At least one of the first supply pipe 21 and the second supply pipe 22 may be connected to the plurality of reaction chambers 20. At this time, the plurality of reaction chambers 20 may include a reaction chamber to which the first supply pipe 21 is connected and a reaction chamber to which the second supply pipe 22 is connected.

The first supply pipe 21 connected to each reaction chamber 20 (each of the reaction chambers 20A to 20H) is provided between the valve 31a and each reaction chamber 20 and a valve 31a that can be switched between open and closed states. And a mass flow controller 32a. That is, the valve 31 a and the mass flow controller 32 a are provided in the first supply pipe 21 so as to correspond to each reaction chamber 20. Similarly, the second supply pipe 22 connected to each reaction chamber 20 has a valve 31b that can be switched between open and closed, and a mass flow controller 32b provided between the valve 31b and each reaction chamber 20. Have. That is, the valve 31b and the mass flow controller 32b are provided corresponding to each reaction chamber 20 in the second supply pipe 22.
In addition, in FIG. 1, in order to facilitate understanding, the valve 31a and the mass flow controller 32a included in the first supply pipe 21 connected to the reaction chamber 20A are denoted by reference numerals and are connected to the reaction chambers 20B to 20H. The reference numerals of the valve 31a and the mass flow controller 32a included in the supply pipe 21 are omitted. The same applies to the valve 31b and the mass flow controller 32b.

In the reaction chambers 20A to 20H, an exhaust pipe 23 is connected to each reaction chamber 20 on the side surface opposite to the side surface to which the supply pipes (the first supply pipe 21 and the second supply pipe 22) are connected. The exhaust pipes 23 connected to the respective reaction chambers 20 join together on the downstream side and are connected to a vacuum pump 26 for exhaust.

The exhaust pipe 23 connected to each reaction chamber 20 has a valve 35 that can be switched between open and closed, and a conductance variable valve 36 provided between the valve 35 and each reaction chamber 20. That is, the valve 35 and the conductance variable valve 36 are provided in the exhaust pipe 23 so as to correspond to each reaction chamber 20.
Note that, in FIG. 1, to facilitate understanding, reference numerals are attached to the valve 35 and the conductance variable valve 36 included in the exhaust pipe 23 connected to the reaction chamber 20A, and the exhaust pipe 23 connected to the reaction chambers 20B to 20H. The reference numerals of the valve 35 and the conductance variable valve 36 included in are omitted.

The operation of the atomic layer deposition apparatus 1 of this embodiment configured as described above when in use will be described.
As a preparatory step when the atomic layer deposition apparatus 1 is used, a roll of the flexible substrate 3 is attached to the unwinding roll 11, one end of which is inserted into the reaction chamber 20A, and the reaction chambers 20A to 20H are sequentially passed. Then, one end of the flexible base material 3 coming out of the reaction chamber 20H is attached to the winding roll 31.
The material of the flexible base material 3 is appropriately determined depending on the laminated body to be produced, and examples thereof include polyethylene terephthalate (PET).

Next, the precursor gas to be used is prepared (accommodated) in each supply unit (first supply unit 27 and second supply unit 28). For example, when performing atomic layer deposition of a metal oxide (for example, aluminum oxide), a gas containing an organic metal gas (for example, trimethylaluminum (TMA)) which is a raw material for forming the atomic layer of the metal oxide is first used. A gas containing oxygen (for example, H ₂ O or the like) for oxidizing the organometallic gas, which is used as the precursor gas, can be used as the second precursor gas. When TMA and H ₂ O are used as precursors, each supply part can usually obtain a sufficient gas pressure even at room temperature.

Further, in this case, the plasma electrode may be arranged in the reaction chamber 20 to which the gas containing at least the second precursor is supplied among the plurality of reaction chambers 20. As a result, an atomic layer made of a metal oxide (eg, aluminum oxide) can be formed by plasma ALD.

Next, the user of the atomic layer deposition apparatus 1 determines the type of precursor gas to be used, the temperature of each reaction chamber 20 (reaction chambers 20A to 20H in this example), and each supply pipe (first supply pipe 21 and second supply pipe 21). The type of gas introduced from the supply pipe 22), gas conditions such as partial pressure and flow rate, the transport speed of the flexible substrate 3 and the like are set in the atomic layer deposition apparatus 1.

Upon completion of these settings, the atomic layer deposition apparatus 1 operates the vacuum pump 26 to evacuate the reaction chambers 20 to bring them into a vacuum state. Then, the temperature conditions of the reaction chambers 20A to 20H are adjusted to the set ranges by a heater as appropriate. A known feedback control or the like may be used for temperature adjustment.

The temperature of each reaction chamber 20 takes into consideration the heat resistance of the flexible substrate 3, the reactivity of the supplied precursor (first precursor or second precursor), the heat resistance of the precursor (pyrolysis temperature), and the like. Selected. For example, when the material of the flexible base material 3 is PET, the heat resistance is 120° C. or lower, and therefore the temperature of the reaction chambers 20A to 20H is set to about 100° C. For example, even if the temperature of each reaction chamber 20 is 100° C., the reaction proceeds in ALD using TMA and H ₂ O as precursor gases.

Subsequently, the atomic layer deposition apparatus 1 controls the opening and closing of the valve 35 and the conductance variable valve 36 connected to each reaction chamber 20 to adjust the internal state of each reaction chamber 20.
For example, when supplying the first precursor gas or the second precursor gas into the reaction chamber 20 (reaction chambers 20A to 20H), the atomic layer deposition apparatus 1 supplies a supply pipe (first The valve (either valve 31a or valve 31b) corresponding to the one supply pipe 21 or the second supply pipe 22) is opened. In this state, referring to the value of the mass flow controller (one of the mass flow controllers 32a and 32b) corresponding to the opened valve, the valve 35 and the conductance variable valve 36 of the exhaust pipe 23 corresponding to each reaction chamber 20 are adjusted. Adjust the exhaust speed.

As a result, each reaction chamber 20 is filled with a desired precursor gas (first precursor gas or second precursor gas), and the gas condition of the precursor gas supplied to each reaction chamber 20 is set within a range. The first precursor gas is adjusted so as not to enter the reaction chamber to which the second precursor gas is supplied. Similarly, the second precursor gas is adjusted so as not to enter the reaction chamber to which the first precursor gas is supplied.

Therefore, the reaction between the first precursor gas and the second precursor gas in each reaction chamber 20 is suppressed, and the deposition of the reactant can be suppressed. Therefore, the atomic layer deposition apparatus 1 can suppress contamination in the reaction chamber. Further, the atomic layer deposition apparatus 1 having the above-described configuration can be used in the reaction chamber without providing a purge zone or the like between the oxidation zone and the zone for introducing the precursor (precursor zone). Since the contamination can be suppressed, the entire apparatus can be downsized as compared with the case where a purge zone or the like is provided.
Furthermore, a small reaction chamber is provided in each reaction chamber 20, the small reaction chamber is filled with a precursor, and the reaction chamber 20 is filled with a purge gas, so that the precursor gas is locally applied to the base material. It is also possible to provide a mechanism for supplying to.

By adjusting the gas conditions described above, each reaction chamber 20A to 20H is adjusted to the optimum exposure condition in the assigned SALD step. In this state, the flexible substrate 3 is conveyed from the unwinding chamber 10 through the reaction chambers 20 toward the winding chamber 30 at a set desired speed, whereby each step of SALD is performed on the flexible substrate 3. Is executed. As a result, an atomic layer made of a desired substance is deposited on the flexible substrate 3 to form a thin film. The flexible base material 3 on which the atomic layer deposition is completed is sequentially wound around the winding roll 31.
According to the atomic layer deposition apparatus 1 of the present embodiment, each of the plurality of reaction chambers 20A to 20H includes the first supply pipe 21 or the second supply pipe 22, so that each reaction chamber 20 is set to the first precursor. Alternatively, the reaction space can be any one of the second precursors. Further, since the exhaust pipe 23 is provided with the conductance variable valve 36, each reaction chamber 20 can be adjusted to a gas condition suitable for the step of SALD, and the inside of the atomic layer deposition apparatus 1 (for example, each It is possible to adjust the gas conditions so as to suppress the deposition of reactants in the reaction chamber 20). Therefore, the atomic layer deposition apparatus 1 according to the present embodiment can form an atomic layer in a suitable manner in accordance with various combinations of precursors and cycle configurations, and can be formed in each apparatus such as in each reaction chamber 20 by a reactant. The device can suppress the contamination.

Further, in the atomic layer deposition apparatus 1 of this embodiment, a purge chamber to which a purge gas is supplied is provided between the reaction chamber to which the first precursor gas is supplied and the reaction chamber to which the second precursor gas is supplied. May be. At this time, the purge gas may not be exhausted from the purge chamber, and the purge gas may be exhausted by the exhaust pipe 23 through each reaction chamber 20 to which the precursor gas (first precursor gas or second precursor gas) is supplied. As for the purge chamber, a part of the plurality of reaction chambers 20 (reaction chambers 20A to 20H) may be used as the purge chamber, or a dedicated purge chamber may be provided. The exhaust pipe may not be provided in the dedicated purge chamber.

As described above, the atomic layer deposition apparatus 1 according to the present embodiment is an atomic layer deposition apparatus that forms an atomic layer on a flexible base material by using the atomic layer deposition method, and the flexible base material 3 is unwound. The take-out chamber 10, the take-up chamber 30 in which the flexible substrate 3 having the atomic layer formed is taken up, and the flexible substrate 3 is provided between the take-out chamber 10 and the take-up chamber 30 so as to pass therethrough. A plurality of reaction chambers 20, a first supply unit 27 containing a gas containing a first precursor, a first supply pipe 21 connected to the first supply unit, and a gas containing a second precursor are stored. A second supply part 28, a second supply pipe 22 connected to the second supply part 28, an exhaust pipe 23 that is connected to each of the plurality of reaction chambers 20 and an exhaust pump, and is capable of adjusting the exhaust amount. At least one of the first supply pipe 21 and the second supply pipe 22 is connected to each of the plurality of reaction chambers 20, and the plurality of reaction chambers to which the gas containing the precursor is supplied is provided. Exhaust is performed from each of 20 through the exhaust pipe 23. Thereby, the atomic layer deposition apparatus 1 can adjust the exhaust amount of each reaction chamber 20, can form a suitable atomic layer, and can suppress contamination in each reaction chamber 20.

Further, the film forming method according to the present embodiment is a film forming method of forming an atomic layer on the flexible base material 3 by a space division atomic layer deposition method (SALD), and the flexible base material 3 is provided so as to pass therethrough. In the film forming method in which the flexible base material 3 passes through the plurality of reaction chambers 20 supplied with the first precursor gas or the second precursor gas to form an atomic layer, the first precursor gas or the second precursor gas Exhaust is performed by an exhaust pipe connected to a plurality of reaction chambers 20 to which the precursor gas is supplied and an exhaust pump. According to the film forming method of the present embodiment, the exhaust amount of each reaction chamber 20 can be adjusted, a suitable atomic layer can be formed, and contamination in each reaction chamber 20 can be suppressed.

(Modification of the first embodiment)
The atomic layer deposition apparatus 1 according to the above-described embodiment further includes, in addition to the first supply unit 27 containing the gas containing the first precursor and the second supply unit 28 containing the gas containing the second precursor, A third supply unit containing a gas containing a third precursor and a third supply pipe connected to the third supply unit are provided, and each of the plurality of reaction chambers 20 has a first supply pipe 21, At least one of the second supply pipe 22 and the third supply pipe may be connected. Thereby, the atomic layer deposition apparatus 1 can form an atomic layer suitably corresponding to various combinations of precursors and cycle configurations.
Further, the third supply unit may contain a purge gas instead of the third precursor. Further, the atomic layer deposition apparatus 1 includes, in addition to the first supply unit 27, the second supply unit 28, and the third supply unit, a purge gas supply unit for containing a purge gas, and a purge gas supply pipe connected to the purge gas supply unit. May be provided.

[Second embodiment]
Next, a second embodiment of the present invention will be described with reference to FIG. The atomic layer deposition apparatus 2 of the present embodiment and the atomic layer deposition apparatus 1 of the first embodiment are different in the exhaust pipe connection mode. The configuration of the atomic layer deposition apparatus 2 is the same as that of the atomic layer deposition apparatus 1 of the above-described first embodiment except the connection mode of the exhaust pipe. For this reason, the atomic layer deposition apparatus 2 similarly exhibits the operational effects of the configuration of the atomic layer deposition apparatus 1 according to the first embodiment and the modification of the first embodiment. In the following description, the same components as those of the atomic layer deposition apparatus 1 described above will be denoted by the same reference numerals and redundant description will be omitted.

FIG. 3 is a schematic view of the internal structure of the atomic layer deposition apparatus 2 according to the second embodiment of the present invention as viewed from above. As shown in FIG. 3, two exhaust pipes, a first exhaust pipe 24 and a second exhaust pipe 25, are connected to the plurality of reaction chambers 20A to 20H, respectively.
The first exhaust pipes 24 connected to the respective reaction chambers 20 join together on the downstream side and are connected to a vacuum pump 26a for exhaust. Further, the second exhaust pipes 25 join together on the downstream side and are connected to a vacuum pump 26b for exhaust different from the vacuum pump 26a.

The first exhaust pipe 24 connected to each reaction chamber 20 has a valve 35a that can be switched between open and closed, and a conductance variable valve 36a provided between the valve 35a and each reaction chamber 20. That is, the valve 35 a and the conductance variable valve 36 a are provided in the first exhaust pipe 24 so as to correspond to each reaction chamber 20. The second exhaust pipe 25 connected to each reaction chamber 20 includes a valve 35b that can be switched between open and closed states, and a conductance variable valve 36b provided between the valve 35b and each reaction chamber 20. Have. That is, the valve 35b and the conductance variable valve 36b are provided in the second exhaust pipe 25 so as to correspond to each reaction chamber 20.

Also in the atomic layer deposition apparatus 2 of the present embodiment, the gas conditions suitable for each step in SALD can be easily adjusted, as in the atomic layer deposition apparatus 1 of the first embodiment.
Further, the atomic layer deposition apparatus 2 includes a first exhaust pipe 24 and a second exhaust pipe 25, and the first exhaust pipe 24 and the second exhaust pipe 25 include corresponding conductance variable valves 36a and 36b, respectively. .. Furthermore, the first exhaust pipe 24 and the second exhaust pipe 25 are connected to independent vacuum pumps 26a and 26b, respectively, which exhaust the reaction chambers 20. Thereby, the atomic layer deposition apparatus 2 can more appropriately adjust the gas conditions in each reaction chamber.

In the atomic layer deposition apparatus 2 of the present embodiment, for example, the reaction chamber to which the first precursor gas is supplied among the plurality of reaction chambers 20A to 20H has the valve 35a of the first exhaust pipe 24 opened and the vacuum pump 26a. The exhaust amount of is adjusted and the conductance variable valve 36a is adjusted. As a result, the desired reaction chamber 20 can be filled with the first precursor gas, and the gas condition of the first precursor gas can be adjusted within the set range. At this time, the second precursor gas is adjusted so as not to enter the reaction chamber to which the first precursor gas is supplied.
Further, in the atomic layer deposition apparatus 2, for example, in the reaction chamber of the reaction chambers 20A to 20H to which the second precursor gas is supplied, the valve 35b of the second exhaust pipe 25 is opened, and the exhaust amount of the vacuum pump 26b is changed. Then, the conductance variable valve 36b is adjusted. As a result, the desired reaction chamber 20 can be filled with the second precursor gas, and the gas condition of the second precursor gas can be adjusted within the set range. At this time, the first precursor gas is adjusted so as not to enter the reaction chamber to which the second precursor gas is further supplied.

Further, in the atomic layer deposition apparatus 2 of the present embodiment, similarly to the first embodiment, between the reaction chamber to which the first precursor gas is supplied and the reaction chamber to which the second precursor gas is supplied, A purge chamber to which the purge gas is supplied may be provided.

Further, according to the atomic layer deposition apparatus 2 of the present embodiment, each of the plurality of reaction chambers 20A to 20H includes the first exhaust pipe 24 and the second exhaust pipe 25, and each exhaust pipe is an independent vacuum pump 26a, Evacuate using 26b. That is, the gas containing the second precursor is not exhausted from the first exhaust pipe 24 connected to the vacuum pump 26a, and the first precursor is contained from the second exhaust pipe 25 connected to the vacuum pump 26b. Gas is not exhausted. Therefore, the atomic layer deposition apparatus 2 can adjust each reaction chamber 20 to which either the first precursor gas or the second precursor gas is supplied to the exhaust condition suitable for the SALD step. .. Also, among the plurality of reaction chambers 20, a reaction chamber to which the first precursor gas is supplied and a reaction chamber to which the second precursor gas is supplied are different exhaust pipes (first exhaust pipe 24 or second exhaust pipe 25). By evacuating by the above, the reaction between the first precursor gas and the second precursor gas in the exhaust pipe can be suppressed. Therefore, the atomic layer deposition apparatus 2 can suppress the deposition of the reactant in the exhaust pipe. Therefore, the atomic layer deposition apparatus 2 according to the present embodiment can adjust the air flow suitable for each step of SALD and can suppress the contamination of the inside of the apparatus such as the reaction chamber and the exhaust pipe by the reactants. ..

As described above, in the atomic layer deposition apparatus 2 according to the present embodiment, the exhaust pipe includes the first exhaust pipe 24 for exhausting the gas containing the first precursor and the first exhaust pipe 24 for exhausting the gas containing the second precursor. There are two exhaust pipes 25, and a first exhaust pipe 24 and a second exhaust pipe 25 are connected to each of the plurality of reaction chambers 20, and each of the first exhaust pipe 24 and the second exhaust pipe 25 is The second exhaust gas is not exhausted from the first exhaust pipe 24, and the first precursor is exhausted from the second exhaust pipe 25. Gas is not exhausted. As a result, the atomic layer deposition apparatus 2 can adjust the air flow suitable for each step of SALD, and suppresses the contamination of the reaction chamber and the exhaust pipe by the reactant, thereby further suppressing the contamination of the internal apparatus. be able to.

Further, the film forming method of the present embodiment is a film forming method in which an atomic layer is formed on the flexible base material 3 by SALD, and the flexible base material 3 is provided so that it can pass therethrough and the first precursor gas or the second precursor gas is used. The flexible base material 3 passes through the plurality of reaction chambers 20 to which the precursor gas is supplied to form an atomic layer, and among the plurality of reaction chambers 20, the reaction chamber to which the first precursor gas is supplied and the second The reaction chamber to which the precursor gas is supplied is exhausted from each independent exhaust pipe by a different exhaust pump for each exhaust pipe, and from the exhaust pipe that exhausts the reaction chamber to which the first precursor gas is supplied, In this film forming method, the second precursor gas is not exhausted, and the first precursor gas is not exhausted from the exhaust pipe that exhausts the reaction chamber to which the second precursor gas is supplied. By the film forming method of the present embodiment, it is possible to adjust the air flow suitable for each step of SALD, and suppress the contamination of the reaction chamber and the exhaust pipe by the reaction product, thereby further suppressing the contamination of the self apparatus. You can

(Modification of the second embodiment)
For example, in the above-described second embodiment, an example in which two exhaust pipes are provided in all the reaction chambers has been described, but all of the plurality of reaction chambers do not necessarily have two exhaust pipes (first exhaust pipe, second exhaust pipe). ) May not be provided. That is, each of the plurality of reaction chambers 20 may be provided with either one of the two exhaust pipes. At this time, each reaction chamber 20 may be provided with, for example, an exhaust pipe corresponding to the precursor gas supplied from the connected supply pipe (first supply pipe or second supply pipe). Further, as an example, when a part of the plurality of reaction chambers is used as a purge chamber, it is not necessary to provide an exhaust pipe in each reaction chamber into which the purge gas is introduced.
Further, the number of exhaust pipes may be further increased according to the gas used. For example, in the second embodiment, when the third precursor is used in addition to the first precursor and the second precursor, the third precursor gas is independent of the first exhaust pipe and the second exhaust pipe. A third exhaust pipe for exhausting the supplied reaction chamber may be provided.

[Example]
Next, an example of the atomic layer deposition apparatus 1 according to the first embodiment of the present invention and setting of each reaction chamber for executing the same will be described using examples.
(Example 1)
Example 1 is an example in which the atomic layer deposition apparatus 1 is used to form an atomic layer made of aluminum oxide on a PET flexible substrate 3 by plasma ALD.
In this example, TMA is used as the first precursor and O ₂ is used as the second precursor. N ₂ is also introduced into each reaction chamber together with the first precursor and the second precursor.
In the first embodiment, TMA and N ₂ are introduced as the first precursor gases into the reaction chambers 20A, 20C, 20E and 20G among the plurality of reaction chambers 20A to 20H. O ₂ and N ₂ are introduced into each of the reaction chambers 20B, 20D, 20F, and 20H as a second precursor gas. A plasma electrode (not shown) is previously arranged in the reaction chamber into which the second precursor gas is introduced, and O ₂ plasma is generated before starting SALD. Further, plasma electrodes may be installed in advance in all the reaction chambers 20 (reaction chambers 20A to 20H), and only the plasma electrodes in the reaction chambers to which O ₂ is supplied may be energized.

In each of the reaction chambers 20A, 20C, 20E, and 20G, the valve 35 is opened to exhaust the first precursor gas through the exhaust pipe 23. Further, in each of the reaction chambers 20B, 20D, 20F, and 20H, the valve 35 is opened to exhaust the second precursor gas through the exhaust pipe 23.
Further, the flow rate of TMA is adjusted by the mass flow controller 32a of the reaction chambers 20A, 20C, 20E and 20G for supplying the first precursor gas, and the opening degree of the conductance variable valve 36 of the reaction chambers 20A, 20C, 20E and 20G is adjusted. Is adjusted so that the exposure amount of TMA is suitable for forming an atomic layer of aluminum oxide and TMA does not enter the reaction chambers 20B, 20D, 20F, and 20H that supply the second precursor gas. , Gas conditions of the reaction chambers 20A, 20C, 20E and 20G are set.
Further, the flow rate of O ₂ is adjusted by the mass flow controller 32b of the reaction chambers 20B, 20D, 20F, and 20H that supply the second precursor gas, and the conductance variable valve 36 of the reaction chambers 20B, 20D, 20F, and 20H is adjusted. By adjusting the opening degree of TMA, plasma suitable for the oxidation of TMA is generated, and in the reaction chambers 20A, 20C, 20E and 20G for supplying the first precursor gas, active species (atomic state) due to O ₂ plasma are generated. The gas conditions of the reaction chambers 20B, 20D, 20F, and 20H are set so that oxygen and the like do not enter.
When the flexible substrate 3 is sent out from the unwinding chamber in this state, first, TMA is chemically adsorbed on the surface of the flexible substrate 3 in the reaction chamber 20A. At this time, the surplus TMA is exhausted together with N ₂ through the exhaust pipe 23 connected to the reaction chamber 20A.

In the subsequent reaction chamber 20B, the TMA chemically adsorbed on the flexible substrate 3 is exposed to O ₂ plasma, and an atomic layer of aluminum oxide is deposited and formed. At this time, the by-product generated by the oxidation of TMA is exhausted together with O ₂ and N ₂ which were not used in the oxidation reaction through the exhaust pipe 23 connected to the reaction chamber 20B. The oxidation reaction can be performed by appropriately determining the size of each reaction chamber 20, the installation position of the plasma electrode, and the connection position of the exhaust pipe 23 according to the diffusion length of the activated species (atomic oxygen, etc.) from the plasma electrode. is there.
Thus, one cycle of SALD is completed by passing through the reaction chambers 20A and 20B. After that, the same steps are repeated, and four cycles of SALD are performed on the flexible substrate 3 before reaching the winding chamber 30.

Next, an example of the atomic layer deposition apparatus 2 according to the second embodiment of the present invention and setting of each reaction chamber for executing the same will be described using a plurality of examples.

(Example 2)
Similar to the first embodiment, the second embodiment is an example in which the atomic layer deposition apparatus 2 is used to form an atomic layer made of aluminum oxide on the flexible base material 3 made of PET by plasma ALD.
In this example, TMA is used as the first precursor and CO ₂ is used as the second precursor. Also, as in Example 1, N ₂ is introduced into each reaction chamber together with the first precursor and the second precursor.
In the second embodiment, TMA and N ₂ are introduced as the first precursor gas into each of the reaction chambers 20A, 20C, 20E, and 20G among the plurality of reaction chambers 20A to 20H. Further, CO ₂ and N ₂ are introduced as the second precursor gas into each of the reaction chambers 20B, 20D, 20F, and 20H.
As in Example 1, a plasma electrode (not shown) is previously placed in the reaction chamber into which the second precursor gas is introduced, and CO ₂ plasma is generated before SALD is started. Alternatively, plasma electrodes may be installed in advance in all the reaction chambers 20 (reaction chambers 20A to 20H) and only the plasma electrodes in the reaction chambers to which the second precursor gas is supplied may be energized.

In each of the reaction chambers 20A, 20C, 20E, and 20G, the valve 35a is opened to exhaust the first precursor gas from the first exhaust pipe 24. In each of the reaction chambers 20B, 20D, 20F, and 20H, the valve 35b is opened and the second precursor gas is exhausted from the second exhaust pipe 25.

Further, the flow rate of TMA is adjusted by the mass flow controller 32a of the reaction chambers 20A, 20C, 20E and 20G for supplying the first precursor gas, and the conductance of the first exhaust pipe 24 of the reaction chambers 20A, 20C, 20E and 20G is adjusted. By adjusting the opening degree of the variable valve 36a, the exposure amount of TMA becomes suitable for forming an atomic layer of aluminum oxide, and the reaction chambers 20B, 20D, 20F, and 20H supplying the second precursor gas have Make settings so that TMA does not enter.
Furthermore, the flow rate of CO ₂ is adjusted by the mass flow controller 32b of the reaction chambers 20B, 20D, 20F, and 20H that supply the second precursor gas, and the second exhaust pipes of the reaction chambers 20B, 20D, 20F, and 20H are used. By adjusting the opening degree of the conductance variable valve 36b of No. 25, plasma suitable for TMA oxidation is generated, and CO ₂ plasma is supplied to the reaction chambers 20A, 20C, 20E and 20G for supplying the first precursor gas. Set so that active species (such as atomic oxygen) do not enter.

When the flexible substrate 3 is sent out from the unwinding chamber in this state, first, TMA is chemically adsorbed on the surface of the flexible substrate 3 in the reaction chamber 20A. At this time, the excess TMA together with N ₂ is exhausted from the first exhaust pipe 24 connected to the reaction chamber 20A. In the subsequent reaction chamber 20B, TMA chemically adsorbed on the flexible substrate 3 is exposed to CO ₂ plasma, and an atomic layer of aluminum oxide is deposited and formed. By-products generated by the oxidation of TMA are exhausted together with CO ₂ and N ₂ which were not used in the oxidation reaction, by the second exhaust pipe 25 connected to the reaction chamber 20B. After that, the same steps are repeated, and four cycles of SALD are performed on the flexible substrate 3 before reaching the winding chamber 30.

(Example 3)
In the third embodiment, in addition to the first supply unit 27 and the second supply unit 28, the third supply unit that stores the purge gas and the third supply unit that supplies the purge gas to the reaction chambers in the third embodiment In this embodiment, a supply pipe is provided and a part of the reaction chamber is used as a purge chamber. The first precursor is TMA as in Example 2, H ₂ O is used as the second precursor, and nitrogen is used as the purge gas.
TMA is introduced as a first precursor gas into each of the reaction chambers 20A and 20E among the plurality of reaction chambers 20A to 20H. H ₂ O is introduced as a second precursor gas into each of the reaction chambers 20C and 20G. Nitrogen is introduced as a purge gas into each of the remaining reaction chambers 20B, 20D, 20F, and 20H.

In this embodiment, the valves 35a and 35b of the reaction chambers of the reaction chambers 20B, 20D, 20F, and 20H, which are purge chambers, are set to be closed. Further, the valves 35a and 35b of the reaction chambers 20A, 20C, 20E and 20G are set to open. That is, by evacuating the reaction chambers 20 other than the purging chamber without evacuating the purging chamber, the reaction chambers 20C and 20G are supplied to the reaction chambers 20A and 20E that supply TMA. Invasion of H ₂ O can be suppressed. Further, similarly, it is possible to suppress the entry of TMA from the reaction chamber 20A and the reaction chamber 20E into the reaction chamber 20C and the reaction chamber 20G that supply H ₂ O.
By setting as described above, the SALD cycle is appropriately repeated for the flexible base material 3 in the atomic layer deposition apparatus 2, and the atomic layer made of aluminum oxide is formed on the flexible base material 3 as in the second embodiment. Can be deposited and formed.

(Example 4)
This embodiment is an example of forming an atomic layer made of a mixed oxide on a PET flexible substrate 3 by using the atomic layer deposition apparatus 2. In this example, the atomic layer deposition apparatus 2 is provided with a third supply unit and a third supply pipe for supplying a third precursor, and TMA is the first precursor, CO ₂ is the second precursor, and bis(diethylamino)silane. (SAM.24) is used as the third precursor.
In the present embodiment, a gas containing the first precursor TMA (first precursor gas) is introduced into each of the reaction chambers 20A and 20E among the plurality of reaction chambers 20A to 20H. It Further, in each of the reaction chambers 20C and 20G, the third precursor SAM. A gas containing 24 (a third precursor gas) is introduced. In addition, a gas (second precursor gas) containing CO ₂ that is the second precursor is introduced into each of the remaining reaction chambers 20B, 20D, 20F, and 20H. A plasma electrode (not shown) is previously arranged in the reaction chamber into which the second precursor gas containing CO ₂ is introduced, and CO ₂ plasma is generated before SALD is started.
With the above settings, the SALD cycle can be appropriately repeated to form an atomic layer of aluminum oxide and silicon oxide on the flexible substrate 3.
Even when SALD of mixed oxides is performed, it is natural that a purge chamber may be provided between the reaction chambers 20.

Although the respective embodiments, modified examples, and examples of the present invention have been described above, the technical scope of the present invention is not limited to the above-described embodiments, and combinations of constituent elements are possible within a range not departing from the spirit of the present invention. It is possible to change, make various changes to each component, or delete.

INDUSTRIAL APPLICABILITY The present invention is applicable to the production of gas barrier films, and specifically, for liquid crystal displays, organic EL displays, organic EL lighting, organic solar cells, electronic components such as semiconductor wafers, and packaging of pharmaceuticals, foods, etc. It can be applied to the production of films and packaging films for precision parts.

1, 2 Atomic layer deposition apparatus 3 Flexible substrate 10 Unwinding chamber 11 Unwinding rolls 20, 20A, 20B, 20C, 20D, 20E, 20F, 20G, 20H Reaction chamber 21 First supply pipe 22 Second supply pipe 23 Exhaust Pipe 24 First exhaust pipe 25 Second exhaust pipe 26, 26a, 26b Vacuum pump 27 First supply unit 28 Second supply unit 30 Winding chambers 31a, 31b, 35 Valves 32a, 32b Mass flow controller 36 Conductance variable valve 31 Winding roll

Claims (10)

An atomic layer deposition apparatus for forming an atomic layer on a flexible substrate using an atomic layer deposition method,
An unwinding chamber in which the flexible base material is unwound,
A winding chamber in which the flexible substrate on which the atomic layer is formed is wound,
Between the unwinding chamber and the winding chamber, a plurality of reaction chambers the flexible substrate is provided to be passable,
A first supply unit containing a gas containing a first precursor;
A first supply pipe connected to the first supply unit,
A second supply unit containing a gas containing a second precursor,
A second supply pipe connected to the second supply unit,
An exhaust pipe that is connected to each of the plurality of reaction chambers and a pump for exhaust and is capable of adjusting the exhaust amount,
Equipped with
At least one of the first supply pipe and the second supply pipe is connected to each of the plurality of reaction chambers,
An atomic layer deposition apparatus, wherein the exhaust pipe exhausts gas from each of the plurality of reaction chambers to which a gas containing the first precursor or the second precursor is supplied. In the exhaust pipe,
A first exhaust pipe for exhausting a gas containing the first precursor;
A second exhaust pipe for exhausting a gas containing the second precursor,
The atomic layer deposition apparatus according to claim 1, wherein the first exhaust pipe and the second exhaust pipe are connected to each of the plurality of reaction chambers. Each of the first exhaust pipe and the second exhaust pipe is configured to perform exhaust using different exhaust pumps,
Gas containing the second precursor is not exhausted from the first exhaust pipe,
The atomic layer deposition apparatus according to claim 2, wherein the gas containing the first precursor is not exhausted from the second exhaust pipe. The atomic layer deposition according to claim 1, wherein a plasma electrode is arranged in a reaction chamber to which a gas containing at least the second precursor is supplied among the plurality of reaction chambers. apparatus. Among the plurality of reaction chambers, a purge chamber to which a purge gas is supplied is provided between a reaction chamber to which the gas containing the first precursor is supplied and a reaction chamber to which the gas containing the second precursor is supplied. It is provided, The atomic layer deposition apparatus of any one of Claim 1 to 4 characterized by the above-mentioned. An atomic layer deposition apparatus for forming an atomic layer on a flexible substrate using an atomic layer deposition method,
An unwinding chamber in which the flexible base material is unwound,
A winding chamber in which the flexible substrate on which the atomic layer is formed is wound,
Between the unwinding chamber and the winding chamber, a plurality of reaction chambers the flexible substrate is provided to be passable,
A first supply unit containing a gas containing a first precursor;
A first supply pipe connected to the first supply unit,
A second supply unit containing a gas containing a second precursor,
A second supply pipe connected to the second supply unit,
A third supply unit containing a gas containing a third precursor,
A third supply pipe connected to the third supply unit,
An exhaust pipe that is connected to each of the plurality of reaction chambers and an exhaust pump and that can adjust the exhaust amount,
Equipped with
At least one of the first supply pipe, the second supply pipe, and the third supply pipe is connected to each of the plurality of reaction chambers,
An atomic layer deposition apparatus comprising: exhausting gas from a reaction chamber supplied with a precursor through the exhaust pipe. A film forming method for forming an atomic layer on a flexible substrate by a space division atomic layer deposition method,
An atomic layer is formed by passing the flexible base material through a plurality of reaction chambers that are provided so that the flexible base material can pass therethrough and are supplied with a gas containing a first precursor or a gas containing a second precursor. ,
A film forming method, wherein exhaust is performed by an exhaust pipe connected to the plurality of reaction chambers supplied with the gas containing the first precursor or the gas containing the second precursor and an exhaust pump. In the film forming method,
Out of the plurality of reaction chambers, the reaction chamber supplied with the gas containing the first precursor and the reaction chamber supplied with the gas containing the second precursor are exhausted from the plurality of independent exhaust pipes. Evacuate using a different pump for each tube,
From the exhaust pipe that exhausts the reaction chamber supplied with the gas containing the first precursor among the plurality of exhaust pipes, the gas containing the second precursor is not exhausted,
The gas containing the first precursor is not exhausted from the exhaust pipe that exhausts the reaction chamber to which the gas containing the second precursor is supplied among the plurality of exhaust pipes. Film forming method. The film forming method according to claim 7, wherein the first precursor contains an organometallic gas. The film forming method according to claim 7, wherein the second precursor contains oxygen.

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