KR102027776B1 - Method for manufacturing pattern using infinite area-selective atomic layer deposition - Google Patents

Abstract

According to the present invention, a method of manufacturing a pattern using atomic layer deposition having infinite selectivity can prevent a deposition material from being deposited in a non-deposition area even when the thickness of the deposited material is infinitely increased and simultaneously deposit a desired material in a deposition area. There is an effect of significantly reducing the time required for deposition. The method includes a surface inactivation step, an atomic layer deposition step, and an etching step.

Description

Method for manufacturing pattern using infinite area-selective atomic layer deposition}

The present invention relates to a method for producing a pattern using a regional selective atomic layer deposition method.

Three-dimensional nanostructures fabricated using 3D patterning technology play a central role in many fields, including fuel cells, data storage devices, sensors, photonics, and microfluidics. For example, various 3D patterning methods have been proposed, such as photolithography, nanoimprinting, near-field scanning optical microscopy (NSOM), and Dip-Pen. However, the conventional method is disadvantageous in that the process is complicated, the use of materials suitable for patterning is not easy, and high process costs are required.

Accordingly, Atomic Layer Deposition (ALD) has been proposed as a simple one-step patterning process with various advantages such as uniformity over a wide area, excellent conformality and excellent thickness controllability. Research is ongoing, and this is a technique that is often used commercially.

However, the atomic layer deposition method as a one-step patterning process alone has a limitation in that it is impossible to implement deposition in the non-deposition region and to deposit the deposition only in the deposition region.

In order to solve this problem, recently, Area-Selective Atomic Layer Deposition (AS-ALD) has been proposed. Regional selective atomic layer deposition has the advantage of directly obtaining a patterned film in which an atomic layer is deposited only in the deposition region except the non-deposition region without a subsequent process. Therefore, regional selective atomic layer deposition has been extensively studied in recent years. For example, regional selective atomic layer deposition has been applied to various fields such as microelectronics, microelectromechanical systems (MEMS), bio / chemical sensors, microfluidics, display units and optoelectronic devices.

In regional selective atomic layer deposition, nonreactive and thermally stable molecules, surface inhibition molecules are used as the passivation layer in the non-deposited areas, thereby theoretically depositing non-deposited areas. The atomic layer will be deposited only in the area. However, there are a variety of factors that limit local selective atomic layer deposition due to the use of surface inhibitory molecules.

For example, due to the various chemical properties of precursors involved in film deposition, the selectivity achieved using a self-assembled monolayer (SAM), a barrier layer formed by surface inhibiting molecules, is only a few depending on the material. Limited to nanometer deposited films. For example, trimethyl aluminum (TMA) is used as a precursor, and the non-deposition region is deactivated with octadecylphosphate (ODPA) as a surface inhibiting molecule to deposit aluminum oxide (Al ₂ O ₃ ) only in the deposition region. In this case, a problem arises in which aluminum oxide starts to be deposited even in non-deposited regions from more than 50 deposition cycles (aluminum oxide thickness of 6 nm). Therefore, it is practically impossible to deposit aluminum oxide with a thickness of more than 6 nm only in the deposition area.

Even this requires more than 48 hours of time for the surface deactivation process to apply surface inhibiting molecules to the non-deposited regions in order to ensure that the deposition material is completely excluded in the non-deposited regions for 50 deposition cycles.

As described above, the conventional method is difficult to deposit deposits exceeding a certain thickness, and there is a disadvantage in that a considerable time is required to deposit the aluminum oxide of the specific thickness.

Therefore, there is a need for a technique that increases the deposition cycle by the required thickness of the deposit, and in particular, even if the thickness is very large, the deposition material is not deposited at all in the non-deposition area and the desired material is deposited only in the deposition area. In addition, the process time required for the deposition also requires a significantly reduced technology compared to the prior art.

KR10-2016-0087348A (2016.07.21)

An object of the present invention is to increase the deposition cycle by the required thickness of the deposit, thereby preventing the deposition material from being deposited at all in the non-deposited area, and at the same time, the pattern using the atomic layer deposition method having an infinite selectivity to deposit the desired material only in the deposition area. It is to provide a method for producing.

Another object of the present invention is to provide a method for producing a pattern using the atomic layer deposition method having an infinite selectivity which significantly reduces the time required for deposition.

The method for producing a pattern according to the present invention comprises the steps of: a) surface deactivation step of applying the surface inhibiting molecule to the non-deposition region of the substrate, b) atomic layer deposition step of depositing the deposit by supplying a precursor to the deposition region of the substrate) and c. Etching step of removing the deposits remaining in the non-deposition region, characterized in that the steps a) to c) is performed repeatedly sequentially to have an infinite selectivity ratio.

In one embodiment of the present invention, when step a) to step c) is sequentially performed, step a) is a surface-activated non-deposited area by removing the surface inhibitory molecules by the etching of step c) And a surface deactivation regeneration step in which the surface inhibitory molecule is reapplied.

In one example of the present invention, in step c), etching may be performed until all deposits present on the entire surface of the non-deposition region are removed.

In one embodiment of the present invention, in the step b), the deposition may be carried out up to a deposition amount such that the deposits present on the entire surface of the non-deposition zone in step c) can be etched and removed. .

In a pattern made according to an example of the present invention, the non-deposition region of the pattern may not include deposits.

In one example of the present invention, the steps a) to c) may be performed in the same reaction space.

In one embodiment of the present invention, the reaction space may be a vacuum state.

In one example of the present invention, in step c), etching may be performed by atomic layer etching.

In one embodiment of the present invention, in step c), the etching may be a wet etching is performed by the etching solution containing the organic acid is in contact with the non-deposition region.

In one embodiment of the invention, the surface of the deposition region may be silicon oxide, the surface of the non-deposition region may include any one or two or more selected from copper, titanium and platinum.

In one embodiment of the invention, the surface inhibiting molecule may comprise an alkane (C6 ~ C18) thiol, the precursor is dialkyl (C1 ~ C5) zinc, trialkyl (C1 ~ C3) aluminum and bis (alkyl (C1-C5) cyclopentadienyl) manganese.

In one embodiment of the present invention, the surface inhibiting molecule may include any one or more selected from alkyl (C12 ~ 24) phosphonic acid and alkyl (C12 ~ 24) trichlorosilane, the precursor is trialkyl (C1 ˜C3) aluminum.

In one embodiment of the present invention, in step c), etching may be performed by contacting the organic acid in the non-deposition region.

According to the present invention, a method of manufacturing a pattern using an atomic layer deposition method having an infinite selectivity ratio does not deposit any deposition material in a non-deposited area even when the thickness of the deposited material is infinitely increased. There is an effect to be deposited.

The method of manufacturing a pattern using the atomic layer deposition method having an infinite selectivity according to the present invention has an effect that the time required for deposition is significantly reduced.

Even if the effects are not explicitly mentioned in the present invention, the effects described in the specification and the inherent effects expected by the technical features of the present invention are treated as described in the specification of the present invention.

1 is a conceptual diagram of a method for producing a pattern using the atomic layer deposition method according to the present invention.
Figure 2 is a data showing the thickness of the deposit according to the deposition cycle in the method for producing a pattern using the atomic layer deposition method according to the present invention.

Hereinafter, a method of manufacturing a pattern using the atomic layer deposition method having an infinite selectivity ratio according to the present invention will be described in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings described herein are provided by way of example in order to fully convey the spirit of the invention to those skilled in the art. Therefore, the present invention is not limited to the drawings presented and may be embodied in other forms, and the drawings may be exaggerated to clarify the spirit of the present invention.

Unless otherwise defined in the technical and scientific terms used herein, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the invention in the following description and the accompanying drawings. The description of well-known functions and configurations that may unnecessarily obscure them will be omitted.

As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the specification indicates otherwise.

As used herein, unless stated otherwise, unit of% means weight% unless otherwise defined.

The method for producing a pattern according to the present invention includes a) a surface deactivation process (SDP) in which surface inhibition molecules are applied to a non-deposition region of a substrate, and b) a precursor is supplied to a deposition region of a substrate. Atomic Layer Deposition (ALD) where the deposit is deposited, and c) Etching (Post Etching, PE) where the deposits remaining in the non-deposition zone are removed, wherein a) to c) are removed. The steps may be performed sequentially sequentially to have infinite selectivity.

As shown in FIG. 1, the non-deposition region of the substrate is surface inactivated through step a) (SDP), and the remaining amount of deposit deposited in the non-deposition region may be minimized in a subsequent step. In particular, the remaining amount of deposits deposited in the non-deposited area in step a) (SDP) and subsequently in step b) is minimized so that a portion of the deposits in the deposition area are subsequently etched away in step c) (PE), The thickness of the deposit increases in proportion to the number of times a) steps SDP, b) ALD and c) steps PE are repeated. That is, when a) step SDP is excluded, all the deposits deposited in the deposition area and the non-deposition area by the etching of step c) during the repetition of each step are substantially removed at the same ratio, The thickness of deposits deposited in the deposition zones does not increase. Therefore, steps a) to c) all proceed sequentially and each step is repeated, thereby providing a method for producing a pattern using the atomic layer deposition method having an infinite selectivity ratio.

In the process of repeating steps a) to c) sequentially, step a) (SDP) is performed by removing the surface inhibitory molecule by the etching of c) step (PE), thereby removing the surface inhibitory molecule in the surface-activated non-deposition region. Surface Deactivation Process Regeneration (SDPR) may be included. That is, step a) (SDPR), which is repeated after step (PE), is characterized by defects (surface activation from which surface inhibitory molecules are removed) that may occur in non-deposited regions by etching of step (PE). It may mean a step to be recovered.

In step a) SDP, the application amount can be adjusted appropriately, but if step a) is a surface deactivation regeneration step, i.e., a) performed again after step a) has been repeated one or more times In the case of step (SDPR), a) a higher quality infinite selection is made that the amount of application of the surface inhibitory molecules of step (SDPR) is less than the amount of application of the surface inhibitory molecules of step a) (SDP), in which no unit repeating process has been performed at all. It may be good in terms of being advantageous for the production of patterns having a ratio.

When steps a) to c) are sequentially repeated, the number of repetitions is adjusted according to the required thickness of the deposit deposited in the deposition area. In particular, the present invention has an effect of increasing the number of repetitions by the required thickness of the deposit at the same time without having any deposit in the non-deposited area as having an infinite selectivity ratio. As a non-limiting example, the required thickness of the deposit may include substantially 1 to 500 nm, specifically 1 to 100 nm, as a typical range of use, but may be beyond this range if necessary.

In addition, in the present invention, although the time required for surface deactivation in step a) (SDP) can be significantly reduced, there is an excellent effect of blocking deposits deposited in non-deposition regions. Conventionally, the surface deactivation process of applying surface inhibiting molecules to non-deposited areas has taken considerable time to ensure that deposition material is completely excluded in non-deposited areas during the deposition cycle. In this conventional case, since the unit repetition process including each of the above-described steps is not recognized, when the time required for the surface deactivation process is drastically reduced, the number of depositions until the first deposition of the deposit in the non-deposition area is deposited. Is significantly reduced. Thus, in the conventional case, since the maximum thickness of the deposit in the deposition area where no deposit is deposited in the non-deposition area is significantly reduced, the problem that the deposition process itself becomes meaningless occurs.

On the other hand, in the present invention, even if the application time of the surface inhibiting molecule in step a) SDP is significantly reduced as described above, the above problem does not occur. As a preferred example, the application time of the surface inhibitory molecule may vary depending on the type and application environment of the surface inhibitory molecule, an etching method described below, for example, 1 hour or less, 10 minutes or less, 1 minute or less. In this case, the lower limit may be selected from a value over a time that may be etched, and may be, for example, 10 seconds. As such, in the present invention, even if the application time is drastically reduced as the etching process of step c) and the repetitive process including the same are continuously performed until the required thickness of the deposit is satisfied, there is no residual deposit in the non-deposition region. There is an effect that the conventional problem that the maximum thickness of the deposit in the deposition area is significantly reduced does not occur.

In the step a) SDP, the coating may be performed in various ways, for example, an immersion method, a spraying method, and the like. At this time, the environmental conditions such as immersion amount, injection amount, injection pressure, injection distance, etc. may refer to the known literature. When the method for producing a pattern according to the present invention is carried out by an automated process, in particular an automated process within a single reaction space, the spraying method may be advantageous, but this is only described as a preferred example, and the present invention is not limited thereto. Of course not.

Other environmental conditions, for example, temperature, humidity, etc. in step a) SDP are not limited because reference can be made to known documents.

In step b) (ALD), the deposition may be such that in step c) (PE) it can be deposited up to a deposition amount below which all deposits present on the entire surface of the non-deposition area can be removed.

As the number of atomic layer depositions in step b) increases, the probability that a nuclei-containing deposit is formed on the surface inhibiting molecules of the non-deposited regions increases, and thus the number of nuclei formed in a portion of the non-deposited regions increases. It can be increased to form a uniform film state in the non-deposited area. The film formed by the nucleus in the non-deposition region may be difficult to remove when the etching of step c) is atomic layer etching described below. Therefore, when the etching of step c) is performed by atomic layer etching described below, it is preferable that the deposition of step b) is preferably performed until the film is formed in the non-deposition region. As a preferred example of the means for this purpose, when the cycle in which one atomic layer is deposited as a unit, it may be preferable to set the cycle to 50 times or less, preferably 20 times or less. In this case, the lower limit value of the period may be selected from a value larger than the atomic layer etching etching period when the period in which one atomic layer is etched is one unit.

Deposition conditions not described above in step b) ALD, for example, precursor exposure time, reaction gas exposure time, inert gas purge time, type of reaction gas, deposition temperature, deposition atmosphere, etc., are determined by atomic layer deposition. , ALD), are not limited because reference is made to literature known in the art.

In step c) PE, etching may be performed by contacting an etching material with the non-deposition region. Substrates comprising a pattern produced by this method have the effect that the deposit is substantially not included in the non-deposition region of the pattern.

In step c), the etching method may be selected from, for example, dry etching using gas, plasma, ion beam, and the like, and wet etching using an etching solution. Preferably, it may be preferable when dry etching is used, and may be preferable since the process becomes easier when the reaction space is the same reaction space. Examples of preferred dry etching include atomic layer etching (ALE). In this case, since the etching time may be formed very short as 60 seconds or less, specifically 1 to 60 seconds, the unit repeating process is performed. There is an easy advantage to this. When wet etching is used, an immersion method or a spraying method may be used. In this case, it is preferable that wet etching is performed by the spraying method in view of easier unit repeating process.

The atomic layer etching is a conventional atomic layer etching process for removing deposits in an ideally layer-by-layer manner through alternating exposure of etch molecules and reactive molecules. It may mean, but in the present invention should be interpreted as etching as a wider range of removal of deposits over nuclei units. In this case, the etching molecules and the reaction molecules used in the etching may be appropriately selected with reference to the known literature depending on the type of deposit to be removed.

When the etching is atomic layer etching, it may be performed by a thermal process (Thermal process). As a preferred example, the etching temperature at the time of atomic layer etching may be good in terms of further increasing the aforementioned effects. In addition, the number of cycles may be appropriately adjusted when the cycle in which one atomic layer is etched is performed in one unit, but the cycle may be 5 times or less, more preferably 3 times or less. It may be good in terms of being able to minimize deposit etch in the deposition area while being removed.

In addition to the foregoing, specific means and environmental conditions of the atomic layer etching may be referred to known literature.

When the etching is a wet etching, the etching material may be an etching solution capable of minimizing the influence on the deposit deposited on the substrate and the deposition region, for example, an organic acid. In one non-limiting example, the organic acid is selected from acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and the like. It may include any one or two or more, and in one preferred embodiment, it may be preferable to include acetic acid. However, this is only described as a preferred example, of course, the present invention is not limited thereto.

The etching time may be longer than the time when all the deposits on the entire surface of the non-deposition area are removed. Since the etching time depends on various environmental conditions such as the kind of precursor, the kind of surface inhibiting molecule, the temperature, and the pressure, the etching time may be appropriately adjusted in consideration of these. As a non-limiting example, the etching time of step c) PE may be 60 minutes or less, 1 second to 60 minutes, 1 to 60 seconds, but may be adjusted according to the etching method and the etching material as described above. Therefore, the present invention should not be construed as being limited thereto.

Etching conditions, such as etching conditions, which are not described above in step (PE), for example, may not be limited because reference may be made to documents known in the etching art.

When the unit repetition process is performed once, the deposition amount (deposition rate) of step b) in the deposition area is greater than the etching amount (etch rate) of step c) in the deposition area, as described above. The non-deposition regions of the pattern have the effect of substantially free of deposits. As a specific example, when the etching of step c) is atomic layer etching, when the unit repeating process is performed once, the number of atomic layers of step b) deposited in the deposition area is etched and removed in the deposition area. c) has an effect of having an infinite selectivity ratio greater than the number of atomic layers in the step.

Steps a) to c) may be preferably performed in the same reaction space (in-situ). Specifically, in the case of a small scale process, it is also possible to perform each step in a different reaction space, and in the case of a large scale process, it may be preferable to be performed in the same reaction space because it may be easily commercially and economically. However, this is only described as a preferred example, of course, the present invention is not limited thereto.

Preferably, the surface inhibiting molecule of step a), the precursor of step b) and the etching material of step c) are supplied to the gas phase. If this is satisfied, since the repeating unit process including steps a) to c) is performed more simply and quickly, the use of the repeating unit process is practically possible, and there is an advantage in terms of volume and commercialization.

In one embodiment of the present invention, the reaction space may be a vacuum state. If this is satisfied, the lower the pressure during deposition, the effect of significantly reducing the amount of deposits present in the non-deposited region to which the surface inhibiting molecules are applied. However, the effect may vary slightly depending on the kind of precursor and the kind of surface inhibiting molecule. In a non-limiting example, when the reaction space is in a vacuum state, all steps may be performed in the reaction space in a vacuum state, and in terms of economy, the reaction space may be in a vacuum state only when step ALD is performed. You can also keep However, this is only described as a preferred example, each step may be carried out at atmospheric pressure or above, and may be performed in a vacuum reaction space independently of each other.

The substrate includes a deposition zone and a non-deposition zone, which may be described herein as a two-dimensional face region in which the deposition zone and the non-deposition zone are partitioned off from each other on the surface. In addition, the substrate may be any material that may include a deposition region and a non-deposition region, which may be referred to since it is widely known in the Atomic Layer Deposition (ALD) art.

The surface of the deposition zone may be any material from which a precursor is supplied to which the deposition material may be deposited, for example silicon oxide. In addition, the surface of the non-deposition region may be any material that can be surface-inactivated by applying a surface inhibiting molecule, for example, a transition metal. The transition metal may include any one or two or more selected from copper, titanium and platinum. However, this is only described as an embodiment, of course, the present invention is not limited thereto.

As used herein, the term "deposit" may refer to a precursor itself, or may refer to a material produced by reacting a precursor with another material such as a reaction gas. For example, when the oxygen atmosphere and the precursor is trialkylaluminum, the deposit deposited in the deposition zone may be aluminum oxide produced by reaction with oxygen, and the deposit deposited in the non-deposition zone may be trialkylaluminum or aluminum oxide. Can be.

When using the method for producing a pattern according to the present invention, even with the use of various kinds of surface inhibiting molecules and precursors, there is no limit that the maximum thickness of the deposit exists without residual deposits in the non-deposition zone, i.e., having infinite selectivity. There is a significant effect. Conventionally, since the degree of repulsive force in which they interact with each other differs according to the kind of precursor and the kind of surface inhibitory molecule, selection of the precursor and surface inhibitory molecule was very important. However, the method of manufacturing a pattern according to the present invention minimizes the influence of the precursor and the surface inhibiting molecule, and thus has infinite selectivity even though various kinds of surface inhibiting molecules and various kinds of precursors can be used in various combinations with each other. It works. This is because the deposition amount of the deposit deposited in the non-deposited area to which the surface inhibiting molecule is applied in step (ALD) is smaller than the deposition amount of the deposit deposited in the deposition area, and c) the residual deposit in the non-deposited area in step (PE) As all are removable, it is due to the principle that the thickness of deposits in the deposition zone is infinitely increased without residual deposits in the non-deposition zone.

As mentioned above, the precursor and the surface inhibiting molecule can be used in Area-Selective Atomic Layer Deposition (AS-ALD) as the repulsive force acts theoretically not coupled to each other electrically, chemically or physically. The present invention may be any material, and the following exemplary embodiments are exemplified in the present specification, but since the present invention is well known, the present invention should not be construed as being limited thereto.

In the first aspect according to the present invention, the surface inhibiting molecule may include an alkane (C6 ~ C18) thiol including dodecanethiol, etc., in this case, the precursor is diethylzinc Dialkyl (C1-C5) zinc, including; Trialkyl (C1-C3) aluminum, including trimethyl aluminum; And bis (alkyl (C1-C5) cyclopentadienyl) manganese, including bis (ethylcyclopentadienyl) manganese (Bis (ethylcyclopentadienyl) manganese) and the like; And the like. However, this is only a specific example, and the present invention is not limited thereto.

In a second aspect according to the present invention, the surface inhibiting molecule is an alkyl (C12-C24) phosphonic acid; Silane-based compounds containing any one or more selected from dialkyl (C1-C3) aminotrialkyl ((C1-C3)) silane and alkyl (C12-C24) trichlorosilane; It may include any one or two or more selected from, and in this case, the precursor may include trialkyl (C1 ~ C3) aluminum. Specifically, examples of the alkyl (C12 to C24) phosphonic acid include octadecyl phosphate (Octadecyl phosphate) and the like, and examples of the dialkyl (C1 to C3) aminotrialkyl ((C1 to C3)) silane dimethylaminotrimethyl Silane (Dimethylaminotrimethylsilane) etc. are mentioned, An example of an alkyl (C12-C24) trichlorosilane is octadecyl trichlorosilane (Octadecyl trichlorosilane), etc. are mentioned. In addition, examples of the precursor include trimethyl aluminum. However, this is only described as a preferred example, of course, the present invention is not limited thereto.

The above-described surface inhibitory molecules and precursors are only described as one embodiment, and according to the technical features of the present invention, since the surface inhibiting molecules and precursors of different embodiments can be used in combination, the present invention is not limited thereto. In addition, various kinds of surface inhibiting molecules and precursors may be used.

In the manufacturing method according to the present invention, various feed materials (precursors, reaction gases) for the formation of deposits may be used, and as long as the feed materials and deposits that can be used in atomic layer deposition are not limited in kind. As a non-limiting example, various materials such as metals such as ruthenium, platinum, titanium, tantalum, alloys such as titanium nitride and tantalum nitride, metal oxides such as aluminum oxide, hafnium oxide, zirconium oxide, and zinc oxide may be used. Can be deposited. However, this is only a specific example, and the present invention is not limited thereto.

Hereinafter, the present invention will be described in detail with reference to Examples, but these are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following Examples.

1. Preparation of Equipment

A silicon substrate covered with a non-deposited region, which is a surface film of copper (Cu) metal, and a deposition region, which is a surface film of silicon oxide (SiO ₂ ), that is, a non-deposited area in which the surface of copper metal and the surface of silicon oxide are partitioned from each other A silicon substrate comprising a metal) and a deposition region (silicon oxide) was prepared. The silicon substrate was immersed in ethanol and then sonicated to remove organic contaminants on the surface.

2. Surface Deactivation Process (SDP)

In the reaction space in a nitrogen atmosphere capable of vacuum, a t-butanol solution containing octadecylphosphonic acid at a concentration of 1 mM was sprayed onto the silicon substrate for 5 minutes, whereby octadecylphosphonic acid, a surface inhibiting molecule, was formed on the silicon substrate. The non-deposition region (copper metal) was surface deactivated by allowing self-assembly to be formed in the non-deposition region (copper metal) of. The surface deactivated silicon substrate was then allowed to dry in the reaction space.

3. Atomic Layer Deposition Process (ALD)

In the reaction space, aluminum oxide (Al ₂ O ₃ ) was deposited in the deposition region (silicon oxide) of the silicon substrate using an atomic layer deposition (ALD) system.

Specifically, the reaction space was converted to a vacuum state of 150 ° C. and 10 ⁻³ torr. Subsequently, after exposing and adsorbing trimethyl aluminum as a precursor to the deposition region (silicon oxide) of the silicon substrate for 5 seconds at a flow rate of 30 sccm, nitrogen (N ₂ ) gas is supplied and purged for 10 seconds at a flow rate of 2,000 sccm for purging. Steps were performed. Subsequently, an oxygen oxide layer was formed on the substrate by exposing the reactant oxygen (O ₂ ) gas at a flow rate of 400 sccm for 5 seconds. A total of ten deposition cycles were performed with one deposition cycle comprising these steps.

4. Etching Process (PE)

In the reaction space, deposits remaining in the non-deposition region (copper metal) of the silicon substrate were removed by an etching process. Specifically, acetic acid was sprayed with the etching solution over the entire area of the silicon substrate for 10 minutes to etch away the deposits remaining in the non-deposition region (copper metal) of the silicon substrate.

5. Repeat process

The surface deactivation process (SDP), atomic layer deposition process (ALD), and etching process (PE) were performed a total of 100 times in one unit to prepare a silicon substrate having a pattern. At this time, each process was performed sequentially. In addition, the surface deactivation process (SDP) in the process of repeating each process is a surface deactivation regeneration process in which octadecylphosphonic acid is reapplied to a non-deposited region (copper metal) from which octadecylphosphonic acid has been removed by etching of the previous process ( SDPR).

In Example 1, except that the etching process (ALE) instead of the etching process (PE) was used in the same manner as in Example 1 to prepare a silicon substrate with a pattern formed of aluminum oxide.

Etching Process (ALE)

In the reaction space, aluminum oxide (Al ₂ O ₃ ) was deposited in the silicon-based deposition region (silicon oxide) using an atomic layer etching (ALD) system.

Specifically, after the step of exposing tin (II) acetylacetonate (Tin (II) acetylacetonate, Sn (acac) ₂ ), which is an etch molecule at 200 ° C., at a partial pressure of 20 mTorr for 5 seconds. , Purge by supplying nitrogen (N ₂ ) gas at a flow rate of 2,000 sccm for 10 seconds. Subsequently, the reaction molecule (Hydrogen fluiride-pyridine, HF-pyridine) is exposed on the substrate at 200 ° C. for 5 seconds at 80 mTorr partial pressure to the non-deposition region of the substrate. All remaining deposits were removed. A total of three etching cycles were performed using a cycle including these steps as one etching cycle.

As a result of elemental analysis of the surface of the silicon substrate on which the pattern was formed, it was confirmed that no aluminum or a compound containing the same was present in the non-deposition region of the silicon substrate. In addition, the silicon substrate was observed through a scanning electron microscope, and it was confirmed that the thickness of the aluminum oxide deposited in the deposition region of the silicon substrate was about 160 nm.

In Example 1, except that dodecanethiol was used instead of octadecylphosphonic acid, the same method as in Example 1 was performed to prepare a silicon substrate having a pattern formed of aluminum oxide.

As a result, in Example 3, as in Example 1, no deposit was present in the non-deposition region of the silicon substrate, and the thickness of aluminum oxide deposited in the deposition region of the silicon substrate was also significantly different from that of Example 1. It was confirmed that it was deposited as the required thickness without difference.

In Example 3, except that diethyl zinc was used instead of trimethylaluminum, a silicon substrate having a pattern formed of zinc oxide was prepared in the same manner as in Example 3.

As a result, in Example 4, as in Example 1, no deposit was present in the non-deposition region of the silicon substrate, and the thickness of the zinc oxide deposited in the deposition region of the silicon substrate was also significantly similar to that of Example 1. It was confirmed that it was deposited as the required thickness without difference.

Comparative Example 1

In Example 1, except that the repeating process was not performed, the same method as in Example 1 was performed to prepare a silicon substrate having a pattern formed of aluminum oxide.

As a result of elemental analysis of the surface of the silicon substrate on which the pattern of Comparative Example 1 was formed, it was confirmed that a large amount of aluminum or a compound containing the same was present in the non-deposition region of the silicon substrate. This result is judged to be due to the fact that the application (injection) time of the surface inhibitory molecules in the surface activation process is significantly shorter than 1 hour, and thus the stability of surface deactivation is not secured.

As such, when the pattern is manufactured by using the method of manufacturing the pattern using the atomic layer deposition method according to the present invention, it can be seen that the pattern having the required thickness can be manufactured by infinitely increasing the deposition cycle.

In particular, in the case of using the method for producing a pattern using the atomic layer deposition method having an infinite selectivity ratio according to the present invention, the surface deactivation process is required to completely exclude the deposition material in the non-deposition region of the substrate even though the surface deactivation process takes very little time. It can be seen that there is no conventional problem that requires more than 48 hours for the process.

Claims (12)

a) surface deactivation step wherein a surface inhibiting molecule is applied to a non-deposited region of the substrate
b) atomic layer deposition in which a precursor is supplied to the deposition zone of the substrate to deposit the deposit;
c) an etching step in which deposits remaining in the non-deposition region are removed
Including;
The method of manufacturing a pattern having an infinite selectivity by repeating steps a) to c) sequentially. The method of claim 1,
When step a) to step c) is sequentially repeated, step a)
Surface inactivation regeneration, whereby the surface inhibitory molecules are removed by etching to reapply the surface inhibitory molecules to the surface-activated non-deposition
Method of producing a pattern comprising a. The method of claim 1,
In step c), etching is performed until all deposits present on the entire surface of the non-deposition zone are removed. The method of claim 3,
In the step b), the deposition is carried out to the deposition amount to the extent that the deposits on the entire surface of the non-deposition area in step c) can be etched and removed all. The method of claim 4, wherein
In the pattern produced, the non-deposition region of the pattern does not include deposits. The method of claim 1,
Step a) to c) is a method for producing a pattern is performed in the same reaction space. The method of claim 6,
And the reaction space is in a vacuum state. The method of claim 1,
In the step c), etching is performed by atomic layer etching. The method of claim 8,
In the step c), the etching is a wet etching method of performing an etching solution containing an organic acid in contact with the non-deposition region. The method of claim 1,
The surface of the deposition zone is silicon oxide,
And the surface of the non-deposition region is a transition metal comprising any one or more selected from copper, titanium and platinum. The method of claim 10,
The surface inhibiting molecule contains an alkane (C6 ~ C18) thiol,
The precursor is a method for producing a pattern selected from dialkyl (C1-C5) zinc, trialkyl (C1-C3) aluminum and bis (alkyl (C1-C5) cyclopentadienyl) manganese. The method of claim 10,
The surface inhibiting molecule includes any one or more selected from alkyl (C12 to C24) phosphonic acid and alkyl (C12 to C24) trichlorosilane,
The precursor is a method for producing a pattern containing trialkyl (C1 ~ C3) aluminum.

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