JP5733507B2 - Deposition method - Google Patents

Description

  The present invention relates to a film forming method. More specifically, the present invention relates to a film forming method for forming a thin film on a substrate using a gas phase, and more particularly, to a film forming method for forming a film while transporting the substrate.

  Methods for forming a thin film using a vapor phase are roughly classified into a chemical vapor deposition (CVD) method and a physical vapor deposition (PVD) method.

  Typical examples of PVD include vacuum evaporation and sputtering. Especially, sputtering is generally expensive, but it can produce high-quality thin films with excellent film quality and film thickness uniformity. Widely applied in fields such as devices.

  CVD is characterized in that a raw material gas is introduced into a vacuum chamber and one or more gases are decomposed or reacted on the substrate by thermal energy to grow a solid thin film. In order to promote the reaction of the gas and / or to lower the reaction temperature of the gas, there are some which use plasma and a catalytic reaction together, which are called PECVD (Plasma Enhanced CVD) and Cat-CVD, respectively. One characteristic of CVD is that it has few film formation defects, and is therefore mainly applied to semiconductor device manufacturing processes such as film formation of gate insulating films. In recent years, atomic layer deposition (ALD) has attracted attention. ALD is a method in which a surface adsorbed substance is deposited one layer at an atomic level by a chemical reaction on the surface, and is classified as one type of CVD. ALD is distinguished from general CVD by CVD, in which a single gas or a plurality of gases are simultaneously used to react a gas on a substrate to grow a thin film, whereas in ALD, a precursor ( Alternatively, an active gas called a precursor (also called a precursor) and a reactive gas (also called a precursor in ALD) are alternately used to form a thin film one layer at an atomic level by adsorption on the substrate surface and subsequent chemical reaction. This is a special film forming method of growing the film. Specifically, in the surface adsorption, when the surface is covered with a certain kind of gas, no further gas adsorption occurs, and the precursor has adsorbed one layer by using the self-limiting effect. Unreacted precursor is evacuated. Next, a reactive gas (also referred to as a second precursor) is introduced, and the precursor is oxidized or reduced to obtain one thin film having a desired composition, and then the reactive gas is exhausted. These are defined as one cycle, and this cycle is repeated to grow a thin film. Therefore, in ALD, the thin film grows two-dimensionally. In addition, ALD is characterized by fewer film-forming defects than conventional CVD and sputtering, as well as conventional vacuum deposition and sputtering, and is expected to be applied in various fields. ing.

  In addition, there is a method of using plasma to activate the reaction in the step of decomposing the second precursor and reacting with the first precursor adsorbed on the substrate, which is a plasma activated ALD (PEALD). : Plasma Enhanced ALD) or simply Plasma ALD.

  ALD technology itself was developed in 1974 by Finnish Dr. Proposed by Tuomo Suntola. The ALD technology is being applied in the semiconductor industry such as the production of gate insulating films because high quality and high density films can be obtained, and is also described in ITRS (International Technology Roadmap for Semiconductors). In addition, since there is a feature that there is no oblique effect compared with other film formation methods, film formation is possible if there is a gap through which gas can enter, as well as line and hole coating with a high aspect ratio, as well as a three-dimensional structure. It is expected to be applied to MEMS (Micro Electro Mechanical Systems) related to the coating of materials.

  However, ALD technology also has drawbacks. For example, the point which uses a special material, its cost, etc. are mentioned. Among them, the biggest drawback is that the film forming speed is slow. Compared with film forming methods such as vacuum deposition and sputtering, the film forming rate is about 5 to 10 times slower.

  The target for forming a thin film using the film forming method as described above is a large plate such as a wafer or a photomask, a large plate such as a glass plate, a non-flexible substrate, a film or the like. There are various types such as a flexible substrate. In response to this, mass production facilities for forming a thin film on these substrates have proposed and put to practical use various substrate handling methods depending on cost, ease of handling, film formation quality, and the like.

  For example, when a wafer is formed, a single substrate is supplied to a film forming apparatus to form a film, and then replaced with the next substrate to form a film again, or a plurality of substrates are set together. There is a batch type in which the same film is formed on all the wafers.

  In the case of forming a glass substrate or the like, there is an in-line type in which film formation is performed simultaneously while sequentially transporting the substrate to a portion serving as a film formation source. Further, when a film is mainly formed on a flexible substrate, there is a so-called roll-to-roll web coating in which the substrate is unwound from a roll, film is formed while being conveyed, and the substrate is wound on another roll. For roll-to-roll web coating, continuous film deposition is performed not only on flexible substrates but also on flexible sheets that can continuously transport substrates to be deposited, or trays that are partially flexible. The method of doing is also included.

  As for any film forming method and substrate handling method, an optimum combination is adopted in consideration of cost, quality, ease of handling, and the like.

  In addition, when forming an optical film or the like, it is necessary to form different types of thin films in multiple layers. In ALD, a film is formed by exposing a precursor over 100 to 200 cycles depending on the film thickness. In such a case, one film forming source is required for one layer in web coating using a flexible substrate (see, for example, Patent Document 1 and Patent Document 2).

International Publication No. 06/093168 Special table 2007-522344

  However, when performing multi-layer film formation in the above-described multilayer film or ALD while transporting the substrate, the conventional method increases the size of the equipment as the number of layers or the number of cycles increases, and the production cost and equipment occupation area are reduced. There is a problem of increasing.

  The present invention has been made in view of such a conventional problem. Even when roll-to-roll film formation is performed, a multilayer film can be efficiently formed. It is an object of the present invention to provide a film forming method capable of increasing the number of cycles and suppressing an increase in equipment size and an increase in occupied area due to multilayering and multiple cycles.

The film forming method of the present invention is a film forming method for forming a thin film on a substrate using a material in a gas phase state while continuously or intermittently transporting the substrate, and comprising an end portion of a rotating drum A substrate transport mechanism provided on the substrate and capable of rotating independently of the rotating drum, placing a portion of the substrate in contact with the substrate and arranging the substrate around the rotating drum; and rotating the rotating drum at a first speed. A step of rotating, a step of supplying each of the at least two materials to the rotating drum, and a step of transporting the substrate at a second speed, wherein the first speed and the second speed are different. It is characterized by that. By having such a configuration, the present invention can efficiently form a multilayer film even in the case of roll-to-roll film formation, and the number of cycles per unit time can be increased in ALD film formation. In addition, it is possible to provide a film forming method capable of suppressing an increase in equipment size and an increase in occupied area due to the increase in the number of layers and the increase in the number of cycles. Further, it is possible to provide a film forming method capable of manufacturing a high quality film at a lower cost.

  Around the rotating drum, it is preferable that the rotating direction of the rotating drum is opposite to the traveling direction of the substrate. Thereby, it is possible to further improve the film forming speed.

  The substrate is preferably a flexible substrate. Thereby, the clearance gap between a rotating drum and a board | substrate can be minimized and a board | substrate can be conveyed smoothly.

  The two materials are preferably different materials. Thereby, the thin film which consists of a different material can be formed and multilayered.

Deposition method, an atomic layer deposition method, using the rotary drum, as a precursor, supplying a first precursor from the first portion of the rotary drum, first the second part of the rotary drum It is preferred to supply a second precursor. Accordingly, at least one layer (one cycle) of film formation can be performed by rotating the rotating drum once.

  Preferably, a third part is provided between the first part and the second part, and a third gas that is not a thin film forming material is introduced from the third part. Thereby, although it does not contribute to the component of the film, it can be effectively used as a gas separating the first precursor release and the second precursor release.

  The third gas is an inert gas, preferably argon. Thereby, the range of the kind of precursor which can be used spreads, and an optimal precursor can be selected from various precursors. Among inert gases, argon can be introduced at a relatively low cost, so that productivity can be increased. Moreover, it can manufacture at lower cost by using nitrogen gas as said 3rd gas.

  The rotating drum has a mechanism for generating or irradiating plasma on a part of the rotating drum, and it is preferable to perform film formation by changing the precursor using the generated or irradiated plasma. Thereby, film formation can be performed efficiently, so that the film formation time can be shortened and the quality of the film can be improved.

  It is preferable that the rotating drum has a flash lamp in a part thereof, and film formation is performed by changing the precursor using heat supplied from the flash lamp. Thereby, the substrate on which the precursor is adsorbed can be heated and the temperature can be controlled relatively easily. Moreover, since radiant heat can be utilized, it is efficient.

  According to the present invention, at least one layer of film can be formed each time the rotating drum makes one rotation. Therefore, even if film formation by roll-to-roll is performed by rotating the rotating drum at a speed faster than the substrate transport speed. The multilayer film can be formed efficiently. Further, in the film formation by ALD, the number of cycles per unit time can be increased, and the increase in the size of equipment and the increase in occupied area due to the increase in the number of layers and the increase in the number of cycles can be suppressed.

Schematic sectional view showing an example of the positional relationship between a precursor and purge gas supply source used in the film forming method of the present invention, and a rotating drum and a film Schematic which shows an example of the positional relationship of the rotating drum and film used for the film-forming method of this invention

  Hereinafter, the film forming method of the present invention will be specifically described with reference to FIGS.

  Here, the film forming apparatus using ALD is mainly described in detail, but the film forming apparatus of the present invention can be similarly applied to a film forming apparatus using CVD, sputtering or other methods. Further, a flexible substrate having flexibility is illustrated as the substrate 103, and a film is representatively used as the flexible substrate. However, even if the substrate is not flexible, such as glass or a wafer, it can be conveyed along a rotating drum. If so, the present invention can be applied. For example, the present invention can be applied to a case where a small substrate is transported while being fixed to a transport sheet. However, the present invention can be most effectively implemented when a flexible substrate is used.

  In film formation by ALD, film formation is often performed in a vacuum. However, it can be performed at atmospheric pressure and is not particularly limited. In the present invention, since a highly reactive precursor is used, a certain chamber for enclosing gas is necessary for implementation, and at least the rotating drum is accommodated therein.

  FIG. 1 is a schematic sectional view showing an example of the positional relationship between a precursor and a third gas (purge gas) supply source used in the film forming method of the present invention, and a rotating drum and a film. FIG. 2 shows the present invention. It is the schematic which shows an example of the positional relationship of the rotating drum used for the film-forming method of, and a film. 2A is a schematic diagram showing an example of the positional relationship between the rotating drum and the film, and FIG. 2B is a diagram in which the substrate 103 is arranged in addition to the configuration of FIG. 2A. Has been. As shown in FIGS. 1, 2 (a), and 2 (b), the rotating drum 100 used in the present invention includes at least a film forming source, that is, a mechanism for discharging a material. For example, in the ALD film forming apparatus, a mechanism for discharging the first precursor and a mechanism for discharging the second precursor are included in one rotating drum 100. Further, the rotating drum 100 may include a mechanism for releasing the third gas. Further, the rotary drum 100 may include a mechanism for exhausting the surplus material or the third gas.

  The precursor is not particularly limited as long as it is in a gas phase at the time of use, and is appropriately selected depending on the film formation type and the film formation temperature. Since the precursor only needs to be in a gas phase at the time of use, the storage state of the precursor may be a liquid phase or a solid phase in addition to the gas phase. For example, when the precursor is in a liquid phase, the precursor is vaporized by a method such as heating or bubbling and then introduced into the rotating drum 100.

  The third gas does not contribute to the constituent components of the film, but is preferably used as a gas separating the first precursor release and the second precursor release. The type of the third gas is not particularly limited as long as it is not a component constituting a thin film obtained by film formation. When nitrogen gas is used as the third gas, a high quality film can be produced at a lower cost, which is preferable. In addition, when a rare gas that is an inert gas is used as the third gas, the range of types of precursors that can be used is widened, and an optimal precursor can be selected from a wide variety of precursors. Among them, argon is preferable from the viewpoint of increasing productivity because it can be introduced as an inert gas at a relatively low cost. In the present invention, as described above, nitrogen gas is defined separately from inert gas.

  A concave portion 101 may be provided in the precursor or barge gas discharge portion of the rotary drum 100. By providing the recess 101, the concentration of the released gas can be uniformly dispersed along the recess 101.

  In the rotating drum 100 shown in FIG. 1, a plurality of recesses 101 are provided, and the first precursor 201, the second precursor, or the third gas 202 is designed to be supplied from the bottom surface of the recesses 101. ing. The first precursor 201, the third gas 202, the second precursor 203, and the third gas 202 (hereinafter, this is repeated) are configured so that the respective recesses 101 are filled with the respective gases. .

  The rotating drum 100 may include a heating mechanism (not shown). In the case where the rotating drum 100 includes a heating mechanism, the reaction between the precursor and the substrate 103 can be promoted by heating the substrate 103 on which the precursor is adsorbed, and the growth of the thin film on the surface of the substrate 103 can be promoted. If a flash lamp (not shown) is used as a heat source, temperature control is relatively easy and radiant heat can be used, which is efficient. In addition, you may provide a water cooling mechanism in the part which does not want to convey heat, and may control temperature.

The rotating drum 100 may include a mechanism (not shown) for generating or irradiating plasma. When the rotating drum 100 includes the mechanism, it is possible to promote the reaction of the precursor and promote the growth of the thin film. In addition, it does not restrict | limit especially as a plasma generation method, In addition to a high frequency (RF) discharge or DC discharge, well-known methods, such as plasma generation by inductive coupling (ICP), are employable. In addition, a mechanism for generating or irradiating plasma can be incorporated in the above-described recess 101.
In ALD, when the first precursor 201 is adsorbed on the substrate 103 and the second precursor 203 reacts with the first precursor 201 adsorbed on the previous substrate 103 to form a thin film, the substrate 103 However, it is desirable that the substrate 103 be exposed to the plasma after or during exposure to the second precursor 203.

  Since the substrate 103 is transported along the rotary drum 100, the film forming apparatus has a substrate transport mechanism 102 corresponding to this. The substrate transport mechanism 102 is designed to be able to rotate independently of the rotating drum 100.

  The clearance (clearance) between the rotating drum 100 and the substrate 103 is preferably as narrow as possible (that is, the substrate 103 is as close as possible to the rotating drum 100). In order to transport the substrate, a part of the substrate 103 is brought into contact with the substrate transport mechanism 102. In order to avoid scratches on the film formation surface of the substrate 103, it is preferable that the substrate transport mechanism 102 in contact with the substrate 103 is at both ends of the rotary drum 100, but the substrate transport mechanism 102 is rotated depending on the size of the substrate 103. A method of preventing the substrate 103 from being bent by arranging it at the center of the drum 100 can also be adopted.

  The rotating drum 100 is rotated at a speed different from the conveyance speed of the substrate 103. Specifically, it is preferable to adjust both speeds so that the rotation speed of the rotary drum 100 is higher than the conveyance speed of the substrate 103. Thereby, the film-forming speed can be increased. The conveyance speed of the substrate 103 is the rotation speed of the substrate conveyance mechanism 102. The optimum speed related to the rotational speed of the rotating drum 100 and the transport speed of the substrate 103 depends on the pressure of the precursor and gas, the temperature, etc., and cannot be determined quantitatively.

  Film formation is performed according to the following procedure.

  As shown in FIGS. 1 and 2B, the substrate 103 is disposed so as to cover the periphery of the rotating drum 102. At this time, the substrate 103 contacts the substrate transport mechanism 102. In order to avoid scratches on the substrate 103, it is desirable that the substrate 103 does not contact the rotating drum 100.

  In the case where a precursor that needs to be heated for film formation is used, when the heating mechanism is provided in the rotating drum 100, a part of the rotating drum 100 is heated using the heating mechanism, and the outside of the rotating drum 100. When a heating mechanism is provided on the chamber wall surface or the like, heating is started using the heating mechanism.

  A precursor and a third gas are supplied to the rotating drum 100. Of the precursor and third gas supplied to the rotating drum 100, the surplus is exhausted.

  The conveyance of the substrate 103 is started and the rotation of the rotary drum 100 is started. At this time, as described above, both speeds are adjusted so that the rotation speed of the rotary drum 100 is faster than the conveyance speed of the substrate 103. Thereby, the film-forming speed can be increased.

  The rotation direction of the rotary drum 100 and the rotation direction of the substrate transport mechanism 102 may be the same direction or may be relatively opposite directions. When the rotation directions of the two are relatively opposite directions, the film forming speed can be increased, which is preferable.

  When the rotation speed of the rotating drum 100 and the rotation speed of the substrate transport mechanism 102 are the same, film formation cannot be performed if the rotation direction is also the same.

  The conveyance of the substrate 103 may be continuous or intermittent.

  According to the present invention, for example, using the configuration shown in FIG. 1, the substrate 103 passes around the rotating drum once (that is, the substrate transport mechanism 102 rotates once), for example, while the rotating drum 100 is rotated 100 times. In this case, while the substrate 103 passes around the rotary drum 100, film formation for 200 layers (for 200 cycles) proceeds on the substrate.

  The present invention relates to a film forming method for forming a thin film on a substrate using a gas phase, and in particular, a film forming method for forming a film while transporting the substrate, and at least one film is formed every time the rotating drum rotates. Therefore, by rotating the rotating drum at a speed faster than the substrate transfer speed, the multilayer film can be formed efficiently even when the film is formed by roll-to-roll. For membranes, the number of cycles per unit time can be increased, and the increase in the size of equipment and the increase in the occupied area due to the increase in the number of layers and the increase in the number of cycles can be suppressed. Can be suitably used.

DESCRIPTION OF SYMBOLS 100 Rotating drum 101 Recessed part 102 Substrate transport mechanism 103 Substrate 110 Roller 201 First precursor 202 Third gas 203 Second precursor

Claims (11)

A film forming method for forming a thin film on a substrate using a material in a gas phase state while continuously or intermittently transporting the substrate,
Placing the substrate around the rotating drum by bringing a part of the substrate into contact with a substrate transport mechanism provided at an end of the rotating drum and capable of rotating independently of the rotating drum;
Rotating the rotating drum at a first speed;
Supplying each of the at least two materials to the rotating drum;
Transporting the substrate at a second speed,
The film forming method, wherein the first speed and the second speed are different.   2. The film forming method according to claim 1, wherein a rotation direction of the rotary drum is opposite to a traveling direction of the substrate around the rotary drum.   3. The film forming method according to claim 1, wherein the substrate is a flexible substrate.   The film forming method according to claim 1, wherein the two materials are different materials. The film formation method is an atomic layer deposition method,
Using the rotating drum, as a precursor, a first precursor is supplied from a first portion of the rotating drum, and a second precursor is supplied from a second portion of the rotating drum. The film-forming method of any one of Claims 1-4. Wherein a third portion provided between the first portion and the second portion, wherein the said third portion, in claim 5, wherein the introducing a third gas not film materials The film forming method.   The film forming method according to claim 6, wherein the third gas is an inert gas.   The film forming method according to claim 7, wherein the inert gas is argon.   The film forming method according to claim 6, wherein the third gas is nitrogen gas. The rotary drum has a mechanism for generating or plasma irradiation in part, to claim 5, characterized in that a film is formed by changing the precursor using the plasma generated or irradiation The film-forming method of description. 11. The film according to claim 5 , wherein the rotating drum has a flash lamp in a part thereof, and performs film formation by changing the precursor using heat supplied from the flash lamp. Film forming method.

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