CN113818007A

CN113818007A - Method and apparatus for filling gaps using atomic layer deposition

Info

Publication number: CN113818007A
Application number: CN202110191386.9A
Authority: CN
Inventors: 赵恩亨; H.李; 李成熙; 李政烨; C.T.阮
Original assignee: Teaching Production And Learning Cooperation Of Incheon University; Samsung Electronics Co Ltd
Current assignee: Teaching Production And Learning Cooperation Of Incheon University; Samsung Electronics Co Ltd
Priority date: 2020-06-19
Filing date: 2021-02-19
Publication date: 2021-12-21
Also published as: KR20210157310A

Abstract

Methods and apparatus for filling gaps using atomic layer deposition are provided. The method includes forming a first reaction-inhibiting layer by adsorbing a reaction-inhibiting agent onto sidewalls of the gap, forming a first precursor layer by adsorbing a first reactant onto a bottom of the gap and sidewalls of the gap around the bottom of the gap, and forming a first atomic layer on the bottom of the gap and the sidewalls of the gap around the bottom of the gap. The reaction inhibitor includes a precursor material that does not react with the second reactant. The first reaction-inhibiting layer has a density gradient in which the density of the reaction-inhibiting agent decreases toward the bottom of the gap. Forming the first atomic layer includes adsorbing a second reactant onto the first precursor layer.

Description

Method and apparatus for filling gaps using atomic layer deposition

Technical Field

The present disclosure relates to methods and/or apparatus for filling gaps using Atomic Layer Deposition (ALD).

Background

Atomic Layer Deposition (ALD) has been used as a process for filling gaps, such as trenches, formed on a substrate. For ALD, surface reactions are utilized. Accordingly, when the gap is filled by using ALD, a filling layer may be formed with a uniform thickness on a surface around the gap, and thus formation of voids may be reduced and/or minimized. However, when the gap has a high aspect ratio, the size of the entrance of the gap may become smaller than the size of the inside of the gap. Therefore, even when ALD is used, voids may be formed.

Disclosure of Invention

One or more embodiments provide methods and/or apparatus for filling gaps using Atomic Layer Deposition (ALD).

Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the embodiments presented in this disclosure.

According to an embodiment, a method of filling a gap formed on a substrate by using Atomic Layer Deposition (ALD) is provided. The method includes forming a first reaction-inhibiting layer by adsorbing a reaction-inhibiting agent onto sidewalls of the gap, the reaction-inhibiting agent including a precursor material that does not react with the second reactant, the first reaction-inhibiting layer having a density gradient in which a density of the reaction-inhibiting agent decreases toward a bottom of the gap; forming a first precursor layer by adsorbing a first reactant to a bottom of the gap and a sidewall of the gap around the bottom of the gap; and forming a first atomic layer on a bottom of the gap and a sidewall of the gap around the bottom of the gap. Forming the first atomic layer includes adsorbing a second reactant onto the first precursor layer.

In some embodiments, the density gradient of the first reaction-inhibiting layer may be determined according to the following equation:

wherein l denotes a depth (nm) of a position of a side wall of the gap on which the reaction inhibitor is adsorbed, w denotes a width (nm) of the gap, P denotes a partial pressure (Pa) of the reaction inhibitor in the reaction chamber, t denotes an exposure time(s) of the reaction inhibitor, m denotes a molecular weight (kg) of the reaction inhibitor, and k denotes a boltzmann constant of 1.38 × 10^-23J/K, and T represents the temperature (K) in the reaction chamber.

In some embodiments, the reaction inhibitor may be substituted with O₃Or O₂And (4) plasma oxidation. The reaction inhibitor can be via O₃Or O₂The plasma treatment converts the material into a first atomic layer.

In some embodiments, the reaction inhibitor may include a central metal and an organic ligand.

In some embodiments, the organic ligand may comprise a cyclopentadienyl (Cp) ligand or a pentamethylcyclopentadienyl (Cp x) ligand.

In some embodiments, the reaction inhibitor may include (Me)₂N)₂SiMe₂、TiCp*(OMe)₃、Ti(CpMe)(OⁱPr)₃、Ti(CpMe)(NMe₂)₃、ZrCp(NMe₂)₃、ZrCp₂Cl₂、Zr(Cp₂CMe₂)Me₂、Zr(Cp₂CMe₂)Me(OMe)、HfCp(NMe₂)₃Or Hf (CpMe) (NMe)₂)₃。

In some embodiments, the reaction inhibitor may have a central metal that is the same as the metal of the first reactant.

In some embodiments, the first reactant can comprise TiCl₄、Ti(OⁱPr)₄、Ti(NMe₂)₄、Ti(NMeEt)₄、Ti(NEt₂)₄、ZrCl₄、Zr(NMe₂)₄、Zr(O^tBu)₄、ZrCp₂Me₂、Zr(MeCp)₂(OMe)Me、HfCl₄、Hf(NMe₂)₄、Hf(NEtMe)₄、Hf(NEt₂)₄、HfCp₂Me₂Or Hf (MeCp)₂(OMe)Me。

In some embodiments, the second reactant may comprise H₂O or O₂。

In some embodiments, the method may further include forming a first fill layer in a bottom-up direction from a bottom of the gap by repeatedly performing a plurality of cycles of forming the first precursor layer and forming the first atomic layer.

In some embodiments, the method may further comprise: forming a second reaction-inhibiting layer on sidewalls of the gap after forming the first filling layer; forming a second precursor layer on an upper surface of the first filling layer and sidewalls of the gap around the upper surface of the first filling layer; and forming a second atomic layer on the upper surface of the first filling layer and the sidewall of the gap around the upper surface of the first filling layer.

In some embodiments, the method may further include forming a second filling layer in a bottom-up direction from an upper surface of the first filling layer by repeatedly performing a plurality of cycles of forming the second precursor layer and forming the second atomic layer.

According to an embodiment, a method of filling a gap formed on a substrate by using Atomic Layer Deposition (ALD) is provided. The method comprises the following steps: forming a first filling layer by sequentially adsorbing a first reactant and a second reactant onto sidewalls and a bottom of the gap; forming a first reaction-inhibiting layer by adsorbing a reaction inhibitor onto the first filling layer formed on the sidewall of the gap, the reaction inhibitor including a precursor material that does not react with the second reactant, the first reaction-inhibiting layer having a density gradient in which a density of the reaction inhibitor decreases toward a bottom of the gap; forming a first precursor layer including adsorbing a first reactant onto a first filling layer formed on and around a bottom of the gap; and forming a first atomic layer on the first filling layer formed on and around the bottom of the gap, the forming the first atomic layer including adsorbing a second reactant onto the first precursor layer.

In some embodiments, the method may further include forming a second fill layer in a bottom-up direction from an upper surface of the first atomic layer, wherein forming the second fill layer may include repeatedly performing a plurality of cycles of forming the first precursor layer and forming the first atomic layer.

After forming the second filling layer, the method may further include: forming a second reaction-inhibiting layer on the first filling layer formed on the sidewall of the gap; forming a second precursor layer on the upper surface of the second filling layer and the first filling layer around the upper surface of the second filling layer; forming a second atomic layer on the upper surface of the second filling layer and the first filling layer around the upper surface of the second filling layer; and forming a third filling layer in a direction from bottom to top from the upper surface of the second filling layer. Forming the third filling layer may include repeatedly performing a plurality of cycles of forming the second precursor layer and forming the second atomic layer.

According to an embodiment, an Atomic Layer Deposition (ALD) apparatus includes: a substrate comprising a plurality of processing regions; and a reactant supply device on the substrate, the reactant supply device configured to fill a gap formed on each of the plurality of processing regions. The reactant supply device may include at least one first supply unit, at least one second supply unit, and at least one third supply unit. The at least one first supply unit may be configured to form a reaction-inhibiting layer on a sidewall of the gap by supplying a reaction-inhibiting agent to the substrate. The at least one second supply unit may be configured to form a precursor layer on the bottom of the gap and sidewalls of the gap around the bottom of the gap by supplying the first reactant to the substrate. The at least one third supply unit may be configured to form the atomic layer on the bottom of the gap and a sidewall of the gap around the bottom of the gap by supplying the second reactant to the substrate. The reaction inhibitor may comprise a precursor material that does not react with the second reactant.

In some embodiments, the ALD apparatus may further comprise a purge unit between adjacent ones of the at least one first supply unit, the at least one second supply unit, and the at least one third supply unit.

In some embodiments, the reaction-inhibiting layer may have a density gradient in which the density of the reaction-inhibiting agent decreases toward the bottom of the gap.

In some embodiments, the density gradient of the reaction-inhibiting layer may be determined according to the rotation speed of the substrate and the number of rotations of the substrate.

According to an embodiment, a method of filling a gap formed on a structure using Atomic Layer Deposition (ALD) is provided. The structure defines the gap and includes a first reaction inhibitor layer including a reaction inhibitor adsorbed onto sidewalls of the gap. The method includes forming a first precursor layer by adsorbing a first reactant onto a first exposed region of a gap, and forming a first atomic layer on the first exposed region of the gap by adsorbing a second reactant onto the first precursor layer. The first exposed region of the gap includes a bottom of the gap and a first portion of a sidewall of the gap around the bottom of the gap. The first reaction-inhibiting layer defines a first exposed region of the gap based on the first reaction-inhibiting layer having a density gradient in which a density of the reaction-inhibiting agent decreases toward a bottom of the gap, such that the first reaction-inhibiting layer exposes a first portion of a sidewall of the gap and the bottom of the gap. The reaction inhibitor includes a precursor material. The second reactant is a material that does not react with the precursor material in the reaction inhibitor.

In some embodiments, the reaction inhibitor may be substituted with O₃Or O₂And (4) plasma oxidation.

In some embodiments, the method may further comprise treating the cell with a compound via O₃Or O₂The plasma treatment converts the reaction inhibitor into a material of the first atomic layer to remove the reaction inhibitor.

In some embodiments, the second reactant may comprise H₂O or O₂。

Drawings

The above and other aspects, features and effects of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings in which:

fig. 1 to 10C are views for describing a method of filling a gap according to an example embodiment;

fig. 11 to 18 are views for describing a method of filling a gap according to other example embodiments;

FIG. 19 is a schematic plan view of an Atomic Layer Deposition (ALD) apparatus according to an example embodiment;

FIG. 20 is a cross-sectional view of the ALD apparatus of FIG. 19, taken along line I-I' of FIG. 19; and

FIG. 21 is a cross-sectional view of the ALD apparatus of FIG. 19, taken along line II-II' of FIG. 19.

Detailed Description

Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. In this regard, the presented embodiments may have different forms and should not be construed as being limited to the description set forth herein. Therefore, only the embodiments are described below to explain aspects by referring to the drawings. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one of … …" when following a column of elements modify the entire column of elements without modifying individual elements in the column.

Hereinafter, example embodiments will be described in detail with reference to the accompanying drawings. In the drawings, like reference numerals denote like elements, and the size of the elements may be exaggerated for clarity and convenience of explanation. The embodiments described hereinafter are merely non-limiting examples, and various modifications may be made based on the embodiments.

Hereinafter, it will be understood that when an element is referred to as being "on" or "over" another element, it can be directly on or under the other element and be directly on the left or right side of the other element, or intervening elements may also be present therebetween. As used herein, the singular terms "a" and "an" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will also be understood that when an element is referred to as being "comprising" or "comprising," the element can include other elements, but not exclude other elements, unless otherwise specified.

The term "the" and other equivalent determinants may correspond to a singular object or a plural object.

Operations may be performed in a suitable order unless specifically described as an order of operations included in the method or otherwise described.

The use of all examples and example terms is intended only to describe the disclosure in detail, and the disclosure is not limited to the examples and example terms, except as they are not limited by the scope of the claims.

Recently, efficient planar superlenses with nanostructures of high precision and high aspect ratio have been developed. High efficiency planar superlenses can be used in a wide variety of fields, such as laser-based microscopes, imaging techniques, spectroscopy techniques, and the like. The method of filling gaps, which will be described hereinafter, may be used as a fabrication technique for super-surface devices requiring nanostructures with high precision and high aspect ratios.

As semiconductor devices become highly integrated, the planar size of discrete devices or interconnects gradually becomes smaller. In contrast, the thickness of layers included in the semiconductor device gradually becomes larger. Further, with the development of multilayer technology for three-dimensionally arranging or connecting discrete devices of semiconductor devices, a large step height may occur on the surface of a process substrate and a deep gap having a high aspect ratio may be formed according to each processing operation. When an interlayer insulating layer is formed on a process substrate having a large step height and a deep gap having a high aspect ratio, a void or the like may be easily formed. A method of filling a gap, which will be described hereinafter, may be applied to the manufacture of a semiconductor device as a technique for filling a deep gap having a high aspect ratio formed in a process substrate.

Further, the method of filling a gap described below may be used in various fields for which forming a thin layer is important, such as: optical sensors including optoelectronic devices, oxygen sensors, optical measurement instruments, and the like, catalysts including hydrogen photocatalysts, catalysts in artificial biotechnology, biomedical materials and devices, and the like.

Fig. 1 to 10C are views for describing a method of filling the gap 150 according to an example embodiment.

In the method of filling the gap 150, according to example embodiments, the first to third reaction-inhibiting

layers

111, 112, and 113 may be formed by adsorbing the reaction-inhibiting agent onto the sidewalls 150a of the gap 150. Next, the first atomic layer 131 may be formed by adsorbing a first reactant as a precursor material and a second reactant as a co-reactant of the first reactant onto the bottom 150b of the gap 150 and around the bottom 150b of the gap 150 through an Atomic Layer Deposition (ALD) process. Thereafter, the first reactant and the second reactant may be repeatedly adsorbed for a plurality of cycles to form the first to third filling layers 141, 142 and 143 in a bottom-up direction from the bottom 150b of the gap 150. Hereinafter, a method of filling a gap according to an example embodiment will be described in detail.

Referring to FIG. 1, a structure, such as a substrate 100, including a gap 150 may be disposed in a reaction chamber (not shown) of an ALD apparatus. Here, the gap 150 in the substrate 100 may have a certain width w and a certain depth h.

The gap 150 may have a high aspect ratio, for example, about 10 or more, but is not limited thereto. Here, the aspect ratio represents a ratio h/w of the depth h of the gap 150 to the width w of the gap 150. The gap 150 may have a width w of, for example, about several tens of nm. As a detailed example, the gap 150 may have a width w of about 20nm to about 100 nm. However, it is only an example, and the width w of the gap 150 may be variously modified.

As shown in fig. 2, a structure in which the material layer 105 having the gap 150 therein is formed on the substrate 100' may be provided in the reaction chamber. For example, the substrate 100' may include silicon, and the material layer 105 may include silicon oxide. In this case, a layer including HfO may be further provided between the substrate 100' and the material layer 105₂An etch stop layer (not shown).

Referring to fig. 3, the first reaction-inhibiting layer 111 may be formed on the sidewalls 150a of the gap 150. The first reaction-inhibiting layer 111 may be formed by adsorbing a reaction-inhibiting agent onto the sidewalls 150a of the gap 150. Here, the reaction inhibitor may include a precursor material that does not react with a second reactant that serves as a co-reactant in the ALD process performed after the first reaction-inhibiting layer 111 is formed.

The first reaction-inhibiting layer 111 may have a density gradient in which the density of the reaction-inhibiting agent decreases from the entrance of the gap 150 toward the bottom 150b of the gap 150. Accordingly, the bottom 150b of the gap 150 and the periphery of the bottom 150b of the gap 150 may not be covered by the first reaction-inhibiting layer 111 and may be exposed.

Hereinafter, the material of the reaction inhibitor will be described.

According to this embodiment, the reaction inhibitor may have basic characteristics similar to those of previous ALD precursors having process compatibility with the ALD process. In detail, the reaction inhibitor may have to have excellent reactivity to have a short exposure time, good volatility to be easily vaporized, and good heat adsorption with respect to the substrate. Furthermore, the reaction inhibitor may have to be thermally stable, volatile by-products that are not reactive have to be produced, and have to be of high purity, economically viable, easy to handle and environmentally friendly so as to be suitable for mass production. Thus, the reaction inhibitor may be selected from previously known ALD precursors, but is not limited thereto.

In addition, the reaction inhibitor may also include the following two characteristics.

First, the reaction inhibitor may pass only through the co-reactant (such as O) which is strongly bound₂Plasma or O₃) Oxidized to become a thin layer. Second, the reaction inhibitor may not react with H used as a co-reactant in the ALD process performed after the formation of the first reaction-inhibiting layer 111₂O or O₂And (4) reacting. As described below, additional characteristics of the reaction inhibitor may be confirmed by measuring contact angle or thickness changes after performing a sequential ALD process.

In the following, comparison is used for formingTiO₂Thin layer ALD precursors of Ti (OMe)₄And TiCp (OMe)₃. Here, Me corresponds to CH₃And Cp corresponds to pentamethylcyclopentadienyl.

When using Ti (OMe)₄When the precursor is used, H₂O as a co-reactant in an ALD process at a temperature of about 300 ℃ or less, and may be present at a temperature of about 0.4 to about 0.4

Per cycle Growth (GPC) for TiO growth₂A thin layer. However, when using TiCp (OMe)₃When the precursor is used, H₂The ALD process with O as a co-reactant may not form TiO₂A thin layer. TiO 2₂The thin layer may be formed by using O only₂Plasma or O₃Formed as a co-reactant.

TiCp*(OMe)₃The precursor can be strongly adsorbed to TiO by H-bonding₂The above. However, it is difficult to form a new Ti — O bond due to steric hindrance of Cp ligands located thereon. In addition, due to its hydrophobicity, Cp ligands may be difficult to pass through with H in the ALD process after forming the first reaction-inhibiting layer 111₂O reacts and oxidizes. However, Cp ligands may be used as the ratio H₂O of a more strongly O coreactant₂Plasma or O₃And oxidized to form a thin layer. Furthermore, TiCp (OMe)₃The precursor may not be adsorbed to pure TiO₂On the surface.

Thus, it was confirmed that TiO was formed using the ALD process₂In the thin-layer process, TiCp (OMe)₃The precursor may have the characteristics of a reaction inhibitor. In detail, when TiCp (OMe)₃The precursor is used as a reaction inhibitor and for forming TiO by using₂When ALD processes are performed with thin layers of ALD precursors, such as tetrakis (dimethylamino) titanium (TDMAT) (which may be substituted with H)₂O oxidation), reaction inhibitor and H₂O may not react with each other in the region coated with the reaction inhibitor, and thus may not form TiO₂Thin layer, and TDMAT and H₂O may react with each other in a region not coated with the reaction inhibitor, and thus may form TiO₂A thin layer. Furthermore, since TiCp (OMe)₃The precursor is not adsorbed to TiO₂So that even if the reaction inhibitor, TiCp (OMe), is repeatedly coated₃The precursor may not be trapped in TiO₂As impurities in the thin layer.

As noted above, the reaction inhibitor may include one or more compounds other than H₂O or O₂A reactive precursor material, wherein, in the ALD process performed after the formation of the first reaction-inhibiting layer 111, H₂O or O₂May be used as a co-reactant.

The reaction inhibitor may include a precursor material comprising a central metal and an organic ligand. Wherein the organic ligand comprises a cyclopentadienyl (Cp) ligand or a pentamethylcyclopentadienyl (Cp) ligand. In this case, when the reaction inhibitor includes a precursor material having the same central metal as the ALD precursor of the material to be filled, impurity trapping due to the reaction inhibitor may be reduced and/or minimized. For example, as described above, when TiCp (OMe)₃The precursor was used as a reaction inhibitor and TDMAT was used to form TiO₂Thin layers of ALD precursors may reduce and/or minimize impurity trapping due to reaction inhibitors.

Table 1 below shows when TiO is formed₂、ZrO₂And/or HfO₂May be used as an example of a material that can be used as a reaction inhibitor.

[ Table 1]

Referring to table 1, it was confirmed that the reaction inhibitor may have the same central metal as the ALD precursor of the thin layer to be formed. The reaction inhibitors described in Table 1 may be reacted with H₂O has low reactivity and thus may not be oxidized.

When coated at atomic layer levelThe reaction inhibitor may not necessarily have the same central metal as the ALD precursor of the thin layer to be formed, while the reaction inhibitor is coated and the amount of trapped impurities does not have a large influence on the performance of the device. In this case, as described with respect to Table 2, a catalyst other than H, for example, may be used₂O or O₂The co-reactant of (a) as a reaction inhibitor. The materials shown in table 2 are examples only, and other precursor materials may be used.

[ Table 2]

The Cp-based precursors used as reaction inhibitors described in Table 2 may react with H due to steric hindrance and hydrophobicity₂O or O₂Are unreactive and may be formed by resorting only to strong co-reactants (such as O)₂Plasma or O₃) The ligands are separated to form a thin layer. Further, even when the reaction inhibitor includes only one atomic layer, the reaction inhibitor may be difficult to adsorb to other precursors due to steric hindrance, and thus, the reaction inhibitor may have barrier properties.

When selecting the material of the reaction inhibitor, the next thing to be considered is the operation of controlling the density of the reaction inhibitor adsorbed onto the side walls of the gap. In the ALD process for the bottom-up gap filling method, the first reaction-inhibiting layer 111 may have to be coated on the wall surface of the gap 150 to have a density gradient in which the density of the reaction inhibitor decreases toward the bottom 150b of the gap 150. In detail, the density of the reaction inhibitor may have to increase around the entrance of the gap 150 and gradually decrease along the sidewall 150a of the gap 150 toward the bottom 150b of the gap 150, so that the reaction inhibitor may not be coated (and/or may be less coated) on the bottom 150b of the gap 150. By adjusting the exposure amount of the reaction inhibitor, the density gradient of the first reaction-inhibiting layer 111 can be obtained.

In detail, the density gradient of the first reaction-inhibiting layer 111 may be determined according to equation 1, which reflects the stoichiometry and the diffusion behavior of molecules.

Here, l denotes a depth nm to a position of the side wall 150a of the gap 150 on which the reaction inhibitor is adsorbed, w denotes a width nm of the gap 150, P denotes a partial pressure Pa of the reaction inhibitor in the reaction chamber, t denotes an exposure time s of the reaction inhibitor, m denotes a molecular mass kg of the reaction inhibitor, and k denotes a Boltzmann constant of 1.38 × 10^-23J/K, T represents the temperature K in the reaction chamber.

In (equation 1), the depth l to the position of the sidewall 150a of the gap 150 on which the reaction inhibitor is adsorbed may be determined by adjusting the exposure amount of the reaction inhibitor (i.e., the product of the partial pressure and the exposure time of the reaction inhibitor). In this case, the density of the reaction inhibitor may increase around the entrance of the gap 150, and may gradually decrease along the sidewall 150a of the gap 150 toward the bottom 150b of the gap 150.

After the first reaction inhibiting layer 111 is formed on the sidewall 150a of the gap 150, a purge process for discharging a material remaining in the reaction chamber to the outside may be performed. The purge process may be by using, for example, N₂Gas, but is not limited thereto.

Referring to fig. 4, a first precursor layer 121 may be formed on the bottom 150b of the gap 150 and around the bottom 150b of the gap 150. The first precursor layer 121 may be formed by adsorbing the first reactant onto the bottom 150b of the gap 150 and around the bottom 150b of the gap 150. As described above, the first reaction-inhibiting layer 111 may be formed to have a density gradient in which the density of the reaction inhibitor decreases toward the bottom 150b of the gap 150. Accordingly, the bottom 150b of the gap 150 and the sidewall 150a therearound may not be coated with the first reaction-inhibiting layer 111 and may be exposed. The first reactant may be adsorbed onto the exposed bottom 150b of the gap 150 and the exposed sidewall 150a around the bottom 150b to form the first precursor layer 121.

The first reactant may comprise a precursor material of the thin layer to be formed. For example,the first reactant may comprise TiCl₄、Ti(OⁱPr)₄、Ti(NMe₂)₄、Ti(NMeEt)₄、Ti(NEt₂)₄、ZrCl₄、Zr(NMe₂)₄、Zr(O^tBu)₄、ZrCp₂Me₂、Zr(MeCp)₂(OMe)Me、HfCl₄、Hf(NMe₂)₄、Hf(NEtMe)₄、Hf(NEt₂)₄、HfCp2Me₂Or Hf (MeCp)₂(OMe) Me. However, the material of the first reactant is not limited thereto. After forming the first precursor layer 121, a purge process may be performed.

Referring to fig. 5, a first atomic layer 131 may be formed on the bottom 150b of the gap 150 and around the bottom 150b of the gap 150. The first atomic layer 131 may be formed by adsorbing the second reactant onto the first precursor layer 121. The second reactant may be a co-reactant and may include, for example, H₂O or O₂. The first atomic layer 131 may include an oxide, a nitride, or a metal, but is not limited thereto.

As described above, the reaction inhibitor may include a precursor material that does not react with the second reactant. Accordingly, the second reactant introduced into the gap 150 may not react with the first reaction-inhibiting layer 111 and may react with the first reactant of the first precursor layer 121 to form the first atomic layer 131. As described above, the first atomic layer 131 may be formed only in a region of the wall surface of the gap 150, which is not coated with the first reaction-inhibiting layer 111, i.e., on the bottom 150b of the gap 150 and the sidewall 150a around the bottom 150 b. After the first atomic layer 131 is formed, a purge process may be performed.

Referring to fig. 6, the first filling layer 141 may be formed to have a certain height in the lower portion of the gap 150 by repeatedly performing adsorption of the first reactant and adsorption of the second reactant for about several tens to several hundreds cycles (e.g., about 30 to 600 cycles). Here, the cycle may include adsorption, purging of the first reactant, adsorption and purging of the second reactant. The first filling layer 141 may be formed in a bottom-up direction from the bottom 150b of the gap 150. The reaction inhibitor may remain on the sidewall 150a of the gap 150, and the sidewall 150a contacts the first filling layer 141.

By repeatedly performing the adsorption of the first reactant and the second reactant, the amount of the first reaction-inhibiting layer 111 on the sidewall 150a of the gap 150 may be gradually reduced, and thus, the barrier property of the first reaction-inhibiting layer 111 may be lowered.

Referring to fig. 7, the second reaction-inhibiting layer 112 may be formed on the sidewalls 150a of the gap 150. The second reaction-inhibiting layer 112 may be formed by adsorbing the reaction-inhibiting agent onto the sidewalls 150a of the gap 150. Here, the second reaction-inhibiting layer 112 may have a density gradient in which the density of the reaction inhibitor decreases from the entrance of the gap 150 toward the first filling-up layer 141. Accordingly, the upper surface of the first filling-up layer 141 and the sidewall 150a of the gap 150 around the first filling-up layer 141 may not be covered by the second reaction-inhibiting layer 112 and may be exposed.

The reaction inhibitor may include one or more of the compounds other than H₂O or O₂A precursor material to which the second reactant of (a) reacts. The material and density adjustment of the reaction inhibitor are described above, and thus the description thereof will be omitted. After the second reaction inhibiting layer 112 is formed, a purging process may be performed.

Referring to fig. 8A, the second precursor layer 122 may be formed on the upper surface of the first filling-up layer 141 and the sidewall 150a of the gap 150 around the first filling-up layer 141. The second precursor layer may be formed by adsorbing the first reactant onto the upper surface of the first filling-up layer 141 exposed through the second reaction-inhibiting layer 112 and the sidewall 150a of the gap 150 around the first filling-up layer 141. Here, as described above, the first reactant may include a precursor material of a thin layer to be formed. After forming the second precursor layer, a purge process may be performed.

Next, referring to fig. 8B, the second atomic layer 132 may be formed on the upper surface of the first filling layer 141 and the sidewall 150a of the gap 150 around the first filling layer 141. The second atomic layer may be formed by adsorbing a second reactant onto the second precursor layer. The second reactant may be a co-reactant and may include, for example, H₂O or O₂. In forming the second precursor layerThereafter, a purge process may be performed.

Next, referring to fig. 8C, the second filling layer 142 may be formed to have a certain height above the first filling layer 141 by repeatedly performing the adsorption of the first reactant and the adsorption of the second reactant for about several tens to several hundreds cycles. Here, the second filling-up layer 142 may be formed in a bottom-up direction from the upper surface of the first filling-up layer 141. As the adsorption of the first reactant and the adsorption of the second reactant are repeatedly performed, the amount of the second reaction-inhibiting layer 112 on the sidewall 150a of the gap 150 may gradually decrease.

Referring to fig. 9, the third reaction-inhibiting layer 113 may be formed on the sidewalls 150a of the gap 150. The third reaction-inhibiting layer 113 may be formed by adsorbing the reaction inhibitor onto the sidewalls 150a of the gap 150. Here, the third reaction-inhibiting layer 113 may have a density gradient in which the density of the reaction inhibitor decreases from the entrance of the gap 150 toward the second packed layer 142. Accordingly, the upper surface of the second filling-up layer 142 and the sidewall 150a of the gap 150 around the second filling-up layer 142 may not be covered by the third reaction-inhibiting layer 113 and may be exposed. After the third reaction-inhibiting layer 113 is formed, a purging process may be performed.

Referring to fig. 10A, the third precursor layer 123 may be formed on the upper surface of the second filling-up layer 142 and the sidewall 150A of the gap 150 around the second filling-up layer 142. The third precursor layer 123 may be formed by adsorbing the first reactant onto the upper surface of the second filling-up layer 142 exposed through the third reaction-inhibiting layer 113 and the sidewall 150a of the gap 150 around the second filling-up layer 142. After forming the third precursor layer, a purge process may be performed. Next, referring to fig. 10B, a third atomic layer 133 may be formed by adsorbing the second reactant onto the third precursor layer. Thereafter, after the third atomic layer 133 is formed, a purge process may be performed.

Referring to fig. 10C, the third filling layer 143 may be formed to have a certain height above the second filling layer 142 by repeatedly performing the adsorption of the first reactant and the adsorption of the second reactant for about several tens to several hundreds cycles. Here, the third filling-up layer 143 may be formed in a bottom-up direction from the upper surface of the second filling-up layer 142.

Accordingly, since the first filling layer 141 to the third filling layer 143 are sequentially formed in the gap 150, a bottom-up gap filling method in which the filling material is filled in the gap 150 in a bottom-up direction from the bottom 150b of the gap 150 can be realized. In the gap filling process described above, the reaction inhibitor remaining in the gap 150 may pass through via O₃Treatment or O₂The plasma treatment becomes a filler material and is removed.

Although fig. 1 to 10C illustrate examples in which the gap 150 is filled with the first to third filling layers 141, 142 and 143, the inventive concept is not limited thereto. The number of filling layers filling the gap 150 may be variously modified.

According to this embodiment, there is no co-reactant (such as H) to be used in a sequential ALD process₂O or O₂) The reacted precursor material may serve as a reaction inhibitor, and a density gradient in which the density of the reaction inhibitor decreases from the entrance of the gap 150 toward the bottom 150b of the gap 150 may be formed, thereby achieving bottom-up gap filling, whereby the gap 150 is filled with a filling material in a bottom-up direction from the bottom 150b of the gap 150.

In addition, the reaction inhibitor may include a precursor material having the same central metal as a precursor for forming a thin layer used in the sequential ALD process, and thus, the trapping of impurities may be limited and/or prevented.

Hereinafter, the reaction inhibitor TiCp will be confirmed based on experiments^*(OMe)₃Adsorption properties, reactivity and barrier properties.

< Experimental example 1> adsorption characteristics of reaction inhibitor

Using TiCp^*(OMe)₃As a reaction inhibitor, and SiO₂The substrate serves as a substrate on which adsorption is performed. In SiO₂Performing the use of TiCp on a substrate^*(OMe)₃The ALD process of (1). In this process, TiCp is contained^*(OMe)₃The temperature of the tank of (a) is about 70 ℃, and the temperature of the reaction chamber is maintainedThe temperature was maintained at 180 ℃.

The cyclic process of adsorption of the reaction inhibitor may include subjecting the SiO₂The substrate is exposed to the reaction inhibitor for a period of time to allow the reaction inhibitor to adsorb to the SiO₂Removing the residual reaction inhibitor which does not participate in the reaction on the substrate through a purging process. Here, the case of samples in which the exposure time of the reaction inhibitor corresponds to 5 seconds(s), 10s, 15s, and 20s is described.

By measuring the contact angle, it can be determined whether or not TiCp (OMe) has been performed₃In SiO₂Adsorption on the substrate. Here, the contact angle means a Water Contact Angle (WCA). WCA is the angle formed tangent to the water droplet at the gas-liquid-solid interface. When not in SiO₂When an additional surface treatment is performed on the substrate, SiO₂The substrate may have a hydrophilic surface. Thus, SiO₂The substrate may have a relatively high surface energy and thus may have a relatively small contact angle. When the reaction inhibitor is not adsorbed to SiO₂On a substrate, on SiO₂The contact angle on the substrate was measured to be 49.2 degrees. By increasing the exposure time of the reaction inhibitor, the contact angle increases. When the exposure time of the reaction inhibitor was 15s, the contact angle had a maximum value of 99.5 degrees, and in this case, it was confirmed that the reaction inhibitor was completely adsorbed to SiO₂On the substrate. Meanwhile, when the exposure time of the reaction inhibitor is increased to more than 15s, the contact angle is slightly decreased. In the case of the sample in which the exposure time of the reaction inhibitor was 15s, the contact angle remained 96.9 degrees after 40 hours, indicating that TiCp^*(OMe)₃Has adsorption stability.

< Experimental example 2> reactivity of reaction inhibitor

Confirming TiCp by performing ALD Process^*(OMe)₃Reactivity with co-reactants. Here, by using TiCp^*(OMe)₃As Ti precursor and using H₂O as a co-reactant performs the ALD process at a temperature of 180 ℃. When a thickness change was detected after performing the ALD process, it was shown to pass TiCp^*(OMe)₃And H₂Reaction between O to form TiO₂A thin layer.

Wherein TiCp^*(OMe)₃The case of samples with exposure times of 1s, 5s, 10s, 15s and 20s is described. As a basis for TiCp^*(OMe)₃As a result of comparing the exposure time with that of the bare substrate, almost no thickness variation was detected. This aspect shows that no TiO formation occurs₂Thin layer, and thus confirmed TiCp^*(OMe)₃Is not associated with H₂Reactivity of O. Thus, when TiCp is used^*(OMe)₃When used as a reaction inhibitor, the reaction inhibitor is reacted with H₂O is not reactive.

< experimental example 3> Barrier Properties of reaction inhibitor

First, by using TDMAT as a Ti precursor on a Si substrate and using H₂O as a co-reactant performs the ALD process at a temperature of 180 ℃. Cycling conditions for the ALD process used herein include TDMAT (1s) -N₂Purge (60s) -H₂O(30s)–N₂And (5) purging (60 s). The ALD process was performed for 250 cycles, and TiO having a thickness of 10nm was formed on the Si substrate₂A thin layer. In TiO₂The contact angle measured on the thin layer was 59.6 degrees.

Next, by passing TiO through₂Thin layer exposure to TiCp^*(OMe)₃15s reaction inhibitor TiCp^*(OMe)₃Coating TiO formed via ALD Process described above₂Thin layer to prepare the first sample. The contact angle measured after the application of the reaction inhibitor was measured to be 99.1 degrees, and thus the surface state change could be confirmed. Further, there is provided a TiO formed not via the ALD process described above₂A thin layer of the second sample being processed.

Thereafter, the ALD process described above is performed again on each of the first and second samples. In the second sample in which the reaction inhibitor was not coated, TiO having a thickness of 10nm₂A thin layer is additionally deposited and the contact angle is measured as the contact angle with the previously formed TiO₂The contact angles of the thin layers are substantially the same. In the first sample in which the reaction inhibitor was coated, the contact angle was measured to be 93.5 degrees, which is larger than that of TiO₂Contact angle of the thin layer. I.e. thereinIn the first sample coated with the reaction inhibitor, no TiO was formed₂A thin layer and the reaction inhibitor remains coated. Thus, it is shown that when TiCp is used^*(OMe)₃When used as a reaction inhibitor, the reaction inhibitor has excellent barrier properties.

Fig. 11 to 18 are views for describing a method of filling a gap according to another example embodiment. The method of filling the gap according to the present embodiment is the same as the method of filling the gap according to the above-described embodiment except for the process of previously forming the first filling layer (241 of fig. 12) in the gap 250.

Referring to FIG. 11, a substrate 200 including a gap 250 may be disposed in a reaction chamber (not shown) of an ALD apparatus. Here, the gap 250 may have a high aspect ratio of about 10 or more, but is not limited thereto.

Referring to fig. 12, the first filling layer 241 may be formed to have a certain thickness on the sidewalls 250a and the bottom 250b of the gap 250 by using an ALD process. First, a precursor layer (not shown) may be formed by adsorbing a first reactant onto the sidewalls 250a and the bottom 250b of the gap 250. The first reactant may comprise a precursor material of the thin layer to be formed. For example, the first reactant may comprise TiCl₄、Ti(OⁱPr)₄、Ti(NMe₂)₄、Ti(NMeEt)₄、Ti(NEt₂)₄、ZrCl₄、Zr(NMe₂)₄、Zr(O^tBu)₄、ZrCp₂Me₂、Zr(MeCp)₂(OMe)Me、HfCl₄、Hf(NMe₂)₄、Hf(NEtMe)₄、Hf(NEt₂)₄、HfCp2Me₂Or Hf (MeCp)₂(OMe) Me. However, the first reactant is not limited thereto. After forming the first precursor layer, a purge process may be performed.

Thereafter, an atomic layer (not shown) may be formed by adsorbing the second reactant onto the precursor layer. An atomic layer may be formed via a reaction between a first reactant and a second reactant. The second reactant may be a co-reactant and may include, for example, H₂O or O₂. Furthermore, can be inA purging process is performed after the first precursor layer is formed.

By repeatedly performing the above-described adsorption of the first reactant and adsorption of the second reactant for several tens to several hundreds cycles, the first filling layer 241 may be formed to have a certain thickness on the sidewalls 250a and the bottom 250b of the gap 250. Here, one cycle may include adsorption, purging of the first reactant, adsorption and purging of the second reactant. The first filling layer 241 may include, for example, an oxide, a nitride, or a metal, but is not limited thereto.

Referring to fig. 13, a first reaction-inhibiting layer 211 may be formed on the first filling-up layer 241 formed on the sidewalls 250a of the gap 250. The first reaction-inhibiting layer 211 may be formed by adsorbing a reaction inhibitor onto the first filling-up layer 241 formed on the sidewalls 250a of the gap 250. Here, the reaction inhibitor may include a precursor material that does not react with the second reactant as a co-reactant. The materials of the reaction inhibitor are described above, and therefore they will not be described again.

The first reaction-inhibiting layer 211 may have a density gradient in which the density of the reaction inhibitor decreases from the entrance of the gap 250 toward the bottom 250b of the gap 250. Here, the density gradient of the first reaction-inhibiting layer 211 may be determined according to equation 1 above. Accordingly, the first filling-up layer 241 formed on and around the bottom 250b of the gap 250 may not be covered by the first reaction-inhibiting layer 211 and may be exposed. The density gradient of the first reaction-inhibiting layer 211 is described above, and thus, the description thereof will be omitted. After the first reaction-inhibiting layer 211 is formed, a purge process for discharging the material remaining in the reaction chamber to the outside may be performed.

Referring to fig. 14, a first precursor layer 221 may be formed on and around the first filling layer 241 formed on the bottom 250b of the gap 250. The first precursor layer 221 may be formed by adsorbing the first reactant to the first filling-up layer 241 formed on the bottom 250b of the gap 250 and the periphery thereof. The first filling layer 241 formed on the bottom 250b of the gap 250 and the region around the first filling layer 241 may not be covered by the first reaction-inhibiting layer 211 and may be exposed. The first reactant may be adsorbed onto the exposed first filling-up layer 241 and the exposed region around the first filling-up layer 241 to form the first precursor layer 221.

The first reactant may comprise a precursor material of the thin layer to be formed. For example, the first reactant may comprise TiCl₄、Ti(OⁱPr)₄、Ti(NMe₂)₄、Ti(NMeEt)₄、Ti(NEt₂)₄、ZrCl₄、Zr(NMe₂)₄、Zr(O^tBu)₄、ZrCp₂Me₂、Zr(MeCp)₂(OMe)Me、HfCl₄、Hf(NMe₂)₄、Hf(NEtMe)₄、Hf(NEt₂)₄、HfCp2Me₂Or Hf (MeCp)₂(OMe) Me, but is not limited thereto. After forming the first precursor layer 221, a purge process may be performed.

Referring to fig. 15, a first atomic layer 231 may be formed on and around a first filling layer 241 formed on the bottom 250b of the gap 250. The first atomic layer 231 may be formed by adsorbing the second reactant onto and around the first filling layer 241 formed on the bottom 250b of the gap 250. The second reactant may be a co-reactant and may include, for example, H₂O or O₂. The first atomic layer 231 may include an oxide, a nitride, or a metal, but is not limited thereto. After the first atomic layer 231 is formed, a purge process may be performed.

Referring to fig. 16, the second filling layer 242 may be formed to have a certain height on the first filling layer 241 by repeatedly performing the adsorption of the first reactant and the adsorption of the second reactant for about several tens to several hundreds cycles. Here, one cycle may include adsorption, purging of the first reactant, adsorption and purging of the second reactant. The second filling-up layer 242 may be formed in a bottom-up direction from the upper surface of the first filling-up layer 241. As the adsorption of the first reactant and the adsorption of the second reactant are repeatedly performed, the amount of the first reaction-inhibiting layer 211 on the sidewall 250a of the gap 250 may gradually decrease.

Referring to fig. 17, a second reaction-inhibiting layer (not shown) may be formed on the first filling-up layer 241 formed on the sidewalls 250a of the gap 250. The second reaction-inhibiting layer may be formed by adsorbing the reaction-inhibiting agent onto the first filling-up layer 241 formed on the sidewalls 250a of the gap 250. After the second reaction inhibiting layer is formed, a purge process may be performed.

Next, after forming a second precursor layer (not shown) by adsorbing the first reactant onto and around the upper surface of the second filling-up layer 242, a purge process may be performed. Further, after forming a second atomic layer (not shown) by adsorbing a second reactant onto the second precursor layer, a purge process may be performed.

The third filling layer 243 may be formed to have a certain height on the second filling layer 242 by repeatedly performing the adsorption of the first reactant and the adsorption of the second reactant for about several tens to several hundreds cycles as described above. Here, the third filling-up layer 243 may be formed in a bottom-up direction from the upper surface of the second filling-up layer 242. As the adsorption of the first reactant and the adsorption of the second reactant are repeatedly performed, the amount of the second reaction-inhibiting layer on the first filling layer 241 formed on the sidewall 250a of the gap 250 may be gradually reduced.

Referring to fig. 18, a third reaction-inhibiting layer (not shown) may be formed on the first filling-up layer 241 formed on the sidewalls 250a of the gap 250. The third reaction-inhibiting layer may be formed by adsorbing the reaction inhibitor onto the first filling-up layer 241 formed on the sidewalls 250a of the gap 250. After the third reaction inhibiting layer is formed, a purging process may be performed.

Next, after forming a third precursor layer (not shown) by adsorbing the first reactant onto the upper surface of the third filling-up layer 243 and the periphery thereof, a purge process may be performed. Further, after a third atomic layer (not shown) is formed by adsorbing the second reactant onto the third precursor layer, a purge process may be performed.

The fourth filling layer 244 may be formed to have a certain height on the third filling layer 243 by repeatedly performing the adsorption of the first reactant and the adsorption of the second reactant for about several tens to several hundreds cycles as described above. Here, the fourth filling-up layer 244 may be formed in a bottom-up direction from the upper surface of the third filling-up layer 243.

According to the present embodiment, the first filling layer 241 may be previously formed to have a certain thickness on the sidewalls 250a and the bottom 250b of the gap 250, and then, the second to fourth filling layers 242 to 244 may be sequentially formed in the gap 250. Therefore, the processing time required for the gap filling process can be reduced.

Hereinafter, an ALD apparatus for performing the method of filling a gap according to the above-described embodiments at high speed will be described.

FIG. 19 is a schematic plan view of an ALD apparatus 500 in accordance with an example embodiment. FIG. 20 is a cross-sectional view of the ALD apparatus 500 of FIG. 19 taken along line I-I 'of FIG. 19, and FIG. 21 is a cross-sectional view of the ALD apparatus 500 of FIG. 19 taken along line II-II' of FIG. 19.

Referring to fig. 19, the ALD apparatus 500 may include a substrate 300 and a reactant supply 400 on the substrate 300. A plurality of processing regions 310 may be provided on the substrate 300, and at least one gap (not shown) to be filled may be formed on each processing region 310. For example, the plurality of processing regions 310 may include a plurality of wafers provided on the substrate 300. The plurality of processing regions 310 may be arranged to have a circular shape externally surrounding the substrate 300. Fig. 19 shows an example in which eight processing regions 310 are provided on a substrate 300. However, the number of processing regions provided on the substrate 300 is not limited thereto, and may be variously modified.

The reactant supply device 400 may be configured to fill the gap by supplying a reactant on the processing region 310 of the substrate 300, and may include at least one first supply unit 411, at least one second supply unit 421, and at least one third supply unit 422. The first supply unit 411, the second supply unit 421, and the third supply unit 422 may each include one or more tanks for storing a reactant, and the reactant supply device may include a pipe (e.g., a pipe) and a pumping system for supplying a reactant and/or a reaction inhibitor to the process region 310 of the substrate 300. The substrate 300 and the reactant supply apparatus 400 may be provided to be relatively rotatable. In general, the reactant supply apparatus 400 may be fixed, and the substrate 300 may be rotatable. For example, the substrate 300 may be on a stage and secured with, for example, an electrostatic chuck, a clamp, and a motor may be configured to rotate the stage. However, the present disclosure is not limited thereto. The substrate 300 may be fixed on a stage, and the reactant supply apparatus 400 may be rotatable. For example, the motor may be configured to rotate the reactant supply.

The at least one first supply unit 411, the at least one second supply unit 421 and the at least one third supply unit 422 may be arranged to have a circular shape along the plurality of processing regions 310. In addition, each purge unit 450 may be provided between the first to

third supply units

411, 421 and 422. The purge unit 450 may include a system for storing a purge gas (e.g., N)₂Argon) and a pumping system for supplying purge gas to the regions of the ALD apparatus 500 between the process regions 310. Fig. 19 shows an example in which the reactant supply device 400 includes two first supply units 411, three second supply units 421, and three third supply units 422 and the purge unit 450 is provided between the first to

third supply units

411, 421, and 422. However, the present disclosure is not limited thereto, and the number of the first to

third supply units

411, 421 and 422 may be variously modified.

Each of the processing regions 310 on the substrate 300 may supply the reaction inhibitor, the first reactant, and the second reactant from the first to

third supply units

411, 421, and 422 via rotation. Therefore, as described above, the gap formed in the processing region 310 may be filled in the bottom-up direction.

Fig. 20 shows the supply of reaction inhibitors to each treatment zone 310. Referring to fig. 20, the first supply unit 411 may supply a reaction-inhibiting agent to each of the process regions 310 of the rotating substrate 300, so that a reaction-inhibiting layer may be formed on sidewalls of the gap. Reaction inhibitors may include, for example, those that do not react with H₂O or O₂The precursor material of the reaction. This aspect is described above, and therefore, the description thereof will be omitted.

Fig. 20 shows an example in which two first supply units 411 supply a reaction suppressor. However, the present disclosure is not limited thereto, and only one of the two first supply units 411 may supply the reaction inhibitor.

A purge unit 450 may be provided around each first supply unit 411. The purge unit 450 may supply, for example, N between the processing regions 310 while the first supply unit 411 supplies the reaction inhibitor to the processing regions 310₂A purge gas of the gas.

The reaction-inhibiting layer formed on the side wall of the gap may have a density gradient in which the density of the reaction inhibitor decreases toward the bottom of the gap as described above. For this reason, it may be necessary to control the exposure time of the treatment region 310 to the reaction-inhibiting agent. The exposure time may be controlled via adjusting the rotation speed and the number of rotations of the substrate 300.

Fig. 21 shows that the first reactant R1 and the second reactant R2 are supplied to each processing region 310 after the reaction-inhibiting layer is formed. Referring to fig. 21, the second supply unit 421 may supply the first reactant R1 to each of the processing regions 310, thereby forming a precursor layer at the bottom of the gap and around the gap. The first reactant R1 may include a precursor material of a thin layer to be formed. In addition, the third supply unit 422 may supply a second reactant to each of the processing regions 310. Here, the second reactant R2 may be a co-reactant and may include, for example, H₂O or O₂. Thus, the second reactant R2 may react with the precursor layer to form an atomic layer at the bottom of the gap and around the gap.

The supply of the first reactant R1 and the second reactant R2 as described above may be simultaneously performed on the processing region 310 of the substrate 300 by the second supply unit 421 and the third supply unit 422. During this process, in order to prevent mixing of the first reactant R1 and the second reactant R2, the purge unit 450 provided around each of the second and

third supply units

421 and 422 may supply a purge gas between the process regions 310.

As described above, by repeatedly supplying the first reactant R1 and the second reactant R2 to the process region 310 of the rotating substrate 300, the inside of the gap formed in the process region 310 can be filled at high speed. Further, since the substrate 300 includes the plurality of processing regions 310 spatially divided, and the gap filling operation can be simultaneously performed on the plurality of processing regions 310, the processing time can be reduced. While one or more embodiments have been described, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope defined by the following claims.

According to the exemplary embodiments described above, non-co-reactants (such as H) are used in sequential ALD processes₂O or O₂) The reacted precursor material may serve as a reaction inhibitor, and a density gradient in which the density of the reaction inhibitor decreases from the entrance of the gap toward the bottom of the gap may be formed, thereby achieving bottom-up gap filling, whereby the gap is filled with a filler material in a bottom-up direction.

In addition, the reaction inhibitor may be formed by using a precursor material having the same central metal as a precursor for forming a thin layer to be used in the sequential ALD process, and thus the trapping of impurities may be limited and/or prevented. The reaction inhibitor can be via O₃Or O₂The plasma treatment is converted into a filling material to be easily removed. Further, after the filling layer is formed to have a certain thickness on the sidewall and the bottom of the gap in advance, other filling layers may be sequentially formed in the gap. Therefore, the time required for gap filling can be reduced.

It is to be understood that the embodiments described herein are to be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should generally be considered as available for other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.

This application claims the benefit of korean patent application No. 10-2020-0075031, filed in the korean intellectual property office on 19/6/2020, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A method of filling a gap formed on a substrate using Atomic Layer Deposition (ALD), the method comprising:

forming a first reaction-inhibiting layer by adsorbing a reaction-inhibiting agent onto sidewalls of the gap, the reaction-inhibiting agent including a precursor material that does not react with a second reactant, the first reaction-inhibiting layer having a density gradient in which a density of the reaction-inhibiting agent decreases toward a bottom of the gap;

forming a first precursor layer by adsorbing a first reactant to the bottom of the gap and a sidewall of the gap around the bottom of the gap; and

forming a first atomic layer on the bottom of the gap and the sidewalls of the gap around the bottom of the gap, the forming the first atomic layer comprising adsorbing the second reactant onto the first precursor layer.

2. The method of claim 1, wherein

Determining the density gradient of the first reaction-inhibiting layer according to the equation:

wherein l represents a depth of a position of the side wall of the gap on which the reaction inhibitor is adsorbed,

w represents the width of the gap and,

p represents the partial pressure of the reaction inhibitor in the reaction chamber,

t represents the exposure time of the reaction inhibitor,

m represents the molecular mass of the reaction inhibitor,

k represents Boltzmann constant of 1.38X 10^-23J/K, and

t represents the temperature in the reaction chamber.

3. The method of claim 1, wherein the reaction inhibitor is O-substituted₃Or O₂And (4) plasma oxidation.

4. The method of claim 1, further comprising:

via O₃Or O₂Plasma treatment converts the reaction inhibitor into the first atomic layer of material.

5. The method of claim 1, wherein the reaction inhibitor comprises a central metal and an organic ligand.

6. The method of claim 5, wherein the organic ligand comprises a cyclopentadienyl (Cp) ligand or a pentamethylcyclopentadienyl (Cp).

7. The method of claim 5, wherein the reaction inhibitor comprises (Me)₂N)₂SiMe₂、TiCp*(OMe)₃、Ti(CpMe)(OⁱPr)₃、Ti(CpMe)(NMe₂)₃、ZrCp(NMe₂)₃、ZrCp₂Cl₂、Zr(Cp₂CMe₂)Me₂、Zr(Cp₂CMe₂)Me(OMe)、HfCp(NMe₂)₃Or Hf (CpMe) (NMe)₂)₃。

8. The method of claim 5, wherein the reaction inhibitor has a central metal that is the same as the metal of the first reactant.

9. The method of claim 1, wherein the first reactant comprises TiCl₄、Ti(OⁱPr)₄、Ti(NMe₂)₄、Ti(NMeEt)₄、Ti(NEt₂)₄、ZrCl₄、Zr(NMe₂)₄、Zr(O^tBu)₄、ZrCp₂Me₂、Zr(MeCp)₂(OMe)Me、HfCl₄、Hf(NMe₂)₄、Hf(NEtMe)₄、Hf(NEt₂)₄、HfCp2Me₂Or Hf (MeCp)₂(OMe)Me。

10. The method of claim 1, wherein the second reactant comprises H₂O or O₂。

11. The method of claim 1, further comprising:

forming a first filling layer in a bottom-up direction from the bottom of the gap by repeatedly performing a plurality of cycles of forming the first precursor layer and forming the first atomic layer.

12. The method of claim 11, further comprising:

forming a second reaction-inhibiting layer on the sidewalls of the gap after forming the first filling-up layer;

forming a second precursor layer on an upper surface of the first filler layer and sidewalls of the gap around the upper surface of the first filler layer; and

forming a second atomic layer on the upper surface of the first filler layer and the sidewall of the gap around the upper surface of the first filler layer.

13. The method of claim 12, further comprising:

forming a second filling layer in the bottom-up direction from the upper surface of the first filling layer by repeatedly performing a plurality of cycles of forming the second precursor layer and forming the second atomic layer.

14. A method of filling a gap formed on a substrate by using Atomic Layer Deposition (ALD), the method comprising:

forming a first filling layer by sequentially adsorbing a first reactant and a second reactant onto sidewalls and a bottom of the gap;

forming a first reaction-inhibiting layer by adsorbing a reaction inhibitor onto the first filling layer formed on the sidewall of the gap, the reaction inhibitor including a precursor material that does not react with the second reactant, the first reaction-inhibiting layer having a density gradient in which a density of the reaction inhibitor decreases toward the bottom of the gap;

forming a first precursor layer comprising adsorbing the first reactant onto the first fill layer formed on and around the bottom of the gap; and

forming a first atomic layer on the first fill layer formed on and around the bottom of the gap, the forming the first atomic layer including adsorbing the second reactant onto the first precursor layer.

15. The method of claim 14, further comprising:

forming a second filling layer in a bottom-up direction from an upper surface of the first atomic layer, wherein

Forming the second fill layer includes repeatedly performing a plurality of cycles of forming the first precursor layer and forming the first atomic layer.

16. The method of claim 15, further comprising:

forming a second reaction-inhibiting layer on the first filling-up layer formed on the sidewall of the gap after forming the second filling-up layer;

forming a second precursor layer on an upper surface of the second filler layer and the first filler layer around the upper surface of the second filler layer;

forming a second atomic layer on the upper surface of the second filler layer and the first filler layer around the upper surface of the second filler layer; and

forming a third filling layer in the bottom-up direction from the upper surface of the second filling layer, the forming the third filling layer including repeatedly performing a plurality of cycles of forming the second precursor layer and forming the second atomic layer.

17. An Atomic Layer Deposition (ALD) apparatus, comprising:

a substrate comprising a plurality of processing regions; and

a reactant supply on the substrate, the reactant supply configured to fill a gap formed on each of the plurality of processing regions,

the reactant supply device comprises at least one first supply unit, at least one second supply unit and at least one third supply unit,

the at least one first supply unit is configured to form a reaction-inhibiting layer on a sidewall of the gap by supplying a reaction-inhibiting agent to the substrate,

the at least one second supply unit is configured to form a precursor layer on a bottom of the gap and a sidewall of the gap around the bottom of the gap by supplying a first reactant to the substrate, the at least one third supply unit is configured to form an atomic layer on the bottom of the gap and the sidewall of the gap around the bottom of the gap by supplying a second reactant to the substrate, and the reaction inhibitor includes a precursor material that does not react with the second reactant.

18. The ALD apparatus of claim 17, further comprising:

a purge unit between adjacent ones of the at least one first supply unit, the at least one second supply unit, and the at least one third supply unit.

19. The ALD apparatus of claim 17, wherein the reaction-inhibiting layer has a density gradient in which a density of the reaction-inhibiting agent decreases toward the bottom of the gap.

20. The ALD device of claim 19, wherein the density gradient of the reaction-inhibiting layer is determined as a function of a rotational speed of the substrate and a number of revolutions of the substrate.

21. A method of filling a gap formed on a structure using Atomic Layer Deposition (ALD), the structure defining the gap and comprising a first reaction inhibitor layer comprising a reaction inhibitor adsorbed onto sidewalls of the gap, the method comprising:

forming a first precursor layer by adsorbing a first reactant onto a first exposed region of the gap, the first exposed region of the gap including a bottom of the gap and a first portion of the sidewall of the gap around the bottom of the gap, the first reaction-inhibiting layer defining the first exposed region of the gap based on the first reaction-inhibiting layer having a density gradient in which a density of the reaction-inhibiting agent decreases toward the bottom of the gap such that the first reaction-inhibiting layer exposes the first portion of the sidewall of the gap and the bottom of the gap, the reaction-inhibiting agent including a precursor material; and

forming a first atomic layer on the first exposed region of the gap by adsorbing a second reactant onto the first precursor layer, the second reactant being a material that does not react with the precursor material in the reaction inhibitor.

22. The method of claim 21, wherein the reaction inhibitor is O-substituted₃Or O₂And (4) plasma oxidation.

23. The method of claim 21, further comprising:

by passing through O₃Or O₂Plasma treatment converts the reaction inhibitor into a material of the first atomic layer to remove the reaction inhibitor.

24. The method of claim 21, wherein

The reaction inhibitor includes a central metal and an organic ligand.

25. The method of claim 21, wherein the second reactant comprises H₂O or O₂。