KR20130105238A - A method of fabricating a semiconductor device - Google Patents

Abstract

PURPOSE: A method for fabricating a semiconductor device is provided to obtain the high degree of integration by forming a deposition layer on a semiconductor substrate. CONSTITUTION: A semiconductor substrate is loaded into a process chamber. A deposition layer is formed on the semiconductor substrate. The semiconductor substrate is unloaded from the process chamber. A preliminary unit layer is formed on the semiconductor substrate (S110). The process chamber is firstly purged (S115). [Reference numerals] (AA) 1 cycle; (BB) Has the desired thickness of a film been reached ?; (S10) Film forming on a semiconductor substrate; (S110) Preliminary unit layer is formed on a semiconductor substrate by supplying a first process material including a film-controlling material and an electrode material to a process chamber; (S115,S125) Process chamber is firstly purged; (S120) Preliminary unit layer is formed into a unit layer by supplying a second process material to the process chamber

Description

A method of fabricating a semiconductor device

The technical idea of the present invention relates to a method of forming a deposited film, a method of manufacturing a semi-structured device using the same, a semiconductor device manufactured thereby, an electronic device and an electronic system employing the same.

In accordance with the trend toward higher integration of semiconductor devices, unexpected problems arise as the size of elements constituting the semiconductor devices is reduced.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a method for forming a deposition film and a method for manufacturing a semiconductor device using the same, which may improve step coverage characteristics.

The technical problem to be solved by the technical idea of the present invention is to provide a deposition film forming method and a method of manufacturing a semiconductor device using the same can improve the uniformity.

Another technical problem to be solved by the technical idea of the present invention is to provide an electronic device and an electronic system including a semiconductor device manufactured by using the manufacturing method of the semiconductor device.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

A method of manufacturing a semiconductor device according to an aspect of the technical idea of the present invention is provided. The method includes loading a semiconductor substrate into a process chamber and forming a deposition film on the semiconductor substrate in the process chamber. Forming the deposition film includes repeatedly forming a unit layer on the semiconductor substrate. The semiconductor substrate on which the deposition film is formed is unloaded from the process chamber. Forming the unit layer supplies a process material comprising a precursor material and a film-control material in the process chamber to form a preliminary unit layer on the semiconductor substrate, wherein the precursor material is bonded to a central atom and the central atom. Wherein the film-controlling material is a hydrogen compound of the ligand of the precursor material, and first purges the process chamber in which the semiconductor substrate having the preliminary unit layer is located, and the first purged process chamber. Forming the preliminary unit layer therein as a unit layer, and second purging the process chamber in which the semiconductor substrate having the unit layer is located.

In some embodiments, the precursor material may be adsorbed onto the semiconductor substrate to form a precursor adsorption layer.

The membrane-controlling material may coordinate with the central atoms of the precursor adsorption layer to form the precursor adsorption layer as a more chemically stable material than the precursor adsorption layer.

In another embodiment, forming the preliminary unit layer supplies the precursor material into the process chamber to form a precursor adsorption layer on the semiconductor substrate, wherein the precursor adsorption layer is combined with a base portion and the base portion. And an adsorption portion, and supplying the membrane-controlled material into the process chamber to separate the superadsorption portion from the base portion.

The membrane-controlling material may break the bond between the superadsorbed portion and the base portion while engaging with the central atom of the superadsorbed portion.

In another embodiment, the preliminary unit layer may include both the precursor material and the film-controlling material.

The ligand of the precursor material and the membrane-controlling material constituting the preliminary unit layer are separated from the preliminary unit layer while forming the preliminary unit layer as the unit layer, and are formed as reaction byproducts, and the reaction byproducts are formed in the process. The chamber may be removed while purging the second purge.

In another embodiment, the ligand comprises a first ligand and a second ligand bonded to the central atom, wherein the first ligand and the second ligand have different formulas, and the membrane-controlling material is It may be a hydrogen compound of one ligand.

There is provided a method of manufacturing a semiconductor device according to another aspect of the technical idea of the present invention. The method includes loading a semiconductor substrate into a process chamber and forming a deposition film on the semiconductor substrate in the process chamber. Forming the deposition film includes repeatedly forming a unit layer on the semiconductor substrate. The semiconductor substrate having the deposition film is unloaded from the process chamber. Forming the unit layer supplies a first film-controlled material into the process chamber to form a surface-controlled layer on the semiconductor substrate, and supplies a precursor material into the process chamber to adsorb to the surface-controlled layer. Forming a precursor adsorption layer to form a preliminary unit layer comprising the surface-control layer and the precursor adsorption layer, wherein the precursor material is a compound comprising a central atom and a ligand bonded to the central atom, and the preliminary unit layer First purging the process chamber in which the semiconductor substrate having the substrate is located, separating the ligand in the surface-control layer and the precursor adsorption layer while forming the preliminary unit layer as a unit layer, and forming a reaction byproduct, And removing the reaction by-products while purging the process chamber in which the semiconductor substrate having the second substrate is located.

In some embodiments, the coordination number of the central atoms in the preliminary unit layer can be greater than the coordination number of the central atoms of the precursor material.

In another embodiment, the supply of the first precursor may begin with the first film-controlled material present in the process chamber.

In another embodiment, after stopping the supply of the first film-controlled material into the process chamber, the precursor material may be supplied into the process chamber.

In another embodiment, while supplying the first film-controlled material into the process chamber, the precursor material may begin to be supplied.

In another embodiment, while supplying the first film-controlled material into the process chamber, supply of the precursor material is stopped before starting supply of the precursor material and stopping supply of the first film-controlled material. You can stop.

In another embodiment, the method may further include supplying a second film-controlled material into the process chamber before stopping the supply of the precursor material into the process chamber and prior to the first purging of the process chamber.

The second film-controlling material may be a material that coordinates with the central atom of the precursor material.

According to another aspect of the inventive concept, a method of manufacturing a semiconductor device is provided. The method includes forming a semiconductor substrate having a structure. The structure has vertical side portions. Loading a semiconductor substrate having the structure into a process chamber and forming a deposition film on the semiconductor substrate having the structure in the process chamber, wherein forming the deposition film repeatedly forms a unit layer on the semiconductor substrate having the structure. It involves doing. The semiconductor substrate having the deposition film is unloaded from the process chamber. The forming of the unit layer may include supplying a first precursor material into the process chamber to form a first preliminary unit layer in which the first precursor material is adsorbed on a semiconductor substrate having the structure, wherein the first preliminary unit layer is A base portion and a supersorption portion physically coupled to the base portion, and supplying a film-controlled material into the process chamber to form the first preliminary unit layer as a second preliminary unit layer, wherein the film-controlled material A part of reacts with the first preliminary unit layer to form a second precursor material while separating the superadsorbed portion from the base portion, and purges the process chamber in which the semiconductor substrate having the second preliminary unit layer is located, Forming the second preliminary unit layer as a unit layer, and purging the process chamber in which the semiconductor substrate having the unit layer is located. .

In some embodiments, the first precursor material is a first compound comprising a central atom and a ligand bonded to the central atom, wherein a portion of the membrane-controlled material is bonded to the central atom of the hyperadsorbed portion to form the superadsorbed portion The second precursor material may be formed while separating from the base portion.

A portion of the membrane-controlling material may combine with the central atoms of the base portion to increase the coordination number of the central atoms of the base portion.

In another embodiment, the semiconductor substrate having the first preliminary unit layer may include an empty region in which the precursor material is not adsorbed.

Forming the second preliminary unit layer may include adsorbing the second precursor material onto the semiconductor substrate of the empty region.

The superadsorption portion may be formed in an upper region of the structure, and the empty region may be formed in a lower region of the structure located at a lower level than the superadsorption portion.

According to another aspect of the inventive concept, a method of manufacturing a semiconductor device is provided. The method includes loading a semiconductor substrate into a process chamber and forming a deposition film on the semiconductor substrate in the process chamber. Forming the deposition film includes repeatedly forming a unit layer on the semiconductor substrate. The semiconductor substrate on which the deposition film is formed is unloaded from the process chamber. Forming the unit layer includes supplying a first process material comprising a film-control material and a precursor material into the process chamber to form a preliminary unit layer, wherein the precursor material is bonded to a central atom and the central atom. A first compound comprising a ligand, wherein the preliminary unit layer comprises a second compound formed by combining the precursor material and the film-controlling material, wherein the preliminary unit layer comprises a process chamber in which a semiconductor substrate having the preliminary unit layer is located. 1 purge and form the preliminary unit layer in the first purged process chamber as a unit layer, wherein the ligand and the membrane in the second compound from the preliminary unit layer are formed while forming the preliminary unit layer as the unit layer. The control material is separated to form a reaction byproduct, and a second process chamber in which the semiconductor substrate having the unit layer is located is placed. While not include removing the reaction by-products.

In some embodiments, during the formation of the preliminary unit layer, precursor molecules of the precursor material combine with each other to form a precursor cluster in the process chamber, and the film-control material is formed between molecules of the precursor cluster. The second compound may be formed by bonding to a molecule of the precursor cluster while breaking the bond.

In another embodiment, forming the preliminary unit layer may include proceeding in a process atmosphere in which the first compound, the film-controlling material, and the second compound coexist.

The details of other embodiments are included in the detailed description and drawings.

According to embodiments of the inventive concept, a method of forming a deposition film and a method of manufacturing a semiconductor device using the same may be provided to improve step coverage characteristics. In addition, according to embodiments of the present invention, there is provided a deposition film formation method that can improve the uniformity of the deposition film on a semiconductor substrate including a structure having a vertical side and a method for manufacturing a semiconductor device using the same can do. In addition, according to embodiments of the inventive concept, it is possible to provide a method capable of improving the uniformity of a deposition film formed on a substrate having a hole having a high aspect ratio.

1 is a process flowchart illustrating a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
2 is a view conceptually illustrating equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept.
3 is a view conceptually illustrating a modified example of equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept.
4 is a view conceptually showing another modified example of equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept.
5 is a view conceptually illustrating another modified example of equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept.
6 is a view conceptually illustrating another modified example of equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept.
7A is a gas pulsing diagram illustrating an example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts.
FIG. 7B is a gas pulsing diagram illustrating another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
FIG. 7C is a gas pulsing diagram illustrating another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
FIG. 7D is a gas pulsing diagram illustrating still another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
FIG. 7E is a gas pulsing diagram illustrating another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
FIG. 7F is a gas pulsing diagram illustrating another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
FIG. 7G is a gas pulsing diagram illustrating another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
FIG. 7H is a gas pulsing diagram illustrating still another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
FIG. 7I is a gas pulsing diagram illustrating another example of a method of supplying a process material into a process chamber to manufacture a semiconductor device according to an example embodiment of the inventive concepts; FIG.
8 is a view conceptually illustrating another modified example of equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept.
9 is a flowchart illustrating a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
10 is a gas pulsing diagram illustrating an example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
11 is a process flowchart illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
12 to 21 are diagrams illustrating examples of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
22 is a gas pulsing diagram illustrating another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
23 is a process flowchart illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
24 to 29 are diagrams illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
30 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
31 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
32 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
33 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
34 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
35 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
36 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept.
37 is a cross-sectional view illustrating an example of a semiconductor device formed by a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
38 is a cross-sectional view illustrating another example of a semiconductor device formed according to a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
39 is a cross-sectional view illustrating still another example of a semiconductor device formed according to a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
40 is a cross-sectional view illustrating still another example of a semiconductor device formed according to a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.
41A to 41C illustrate a portion of a semiconductor device manufactured according to an example of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept.
42A to 42C illustrate portions of a semiconductor device manufactured according to another example of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept.
43A to 43C illustrate a portion of a semiconductor device manufactured according to still another example of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept.
44A to 44C illustrate portions of a semiconductor device manufactured according to yet another example of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept.
45A to 45C illustrate portions of a semiconductor device manufactured according to still another example of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept.
46 is a schematic diagram illustrating a memory card having a semiconductor device manufactured according to example embodiments of the inventive concepts.
47 is a block diagram illustrating an electronic system having a semiconductor device manufactured according to example embodiments of the inventive concepts.
48 is a block diagram illustrating a data storage device having a semiconductor device manufactured according to example embodiments of the inventive concept.
49 is a diagram illustrating an electronic system according to an embodiment of the inventive concept.
50 is a diagram schematically illustrating a mobile wireless phone including a semiconductor device manufactured according to embodiments of the inventive concept.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. It is intended that the scope of the invention be defined by the claims and the equivalents thereof. The dimensions and relative sizes of layers and regions in the figures may be exaggerated for clarity of illustration. Like reference numerals refer to like elements throughout.

The embodiments described herein will be described with reference to cross-sectional views, plan views, and block diagrams, which are ideal schematics of the present invention. Accordingly, shapes of the exemplary drawings may be modified by manufacturing techniques and / or tolerances. Accordingly, the embodiments of the present invention are not limited to the specific forms shown, but also include variations in forms generated by the manufacturing process. Thus, the regions illustrated in the figures have schematic attributes, and the shapes of the regions illustrated in the figures are intended to illustrate specific types of regions of the elements and are not intended to limit the scope of the invention.

In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Also, when a layer is referred to as being "on" another layer or substrate, it may be formed directly on another layer or substrate, or a third layer may be interposed therebetween. Like numbers refer to like elements throughout the specification.

The terms first, second, etc. may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may be referred to as a first component.

Terms such as top, bottom, top, bottom, or top, bottom, etc. are used to distinguish relative positions in components. For example, in the case of naming the upper part of the drawing as upper part and the lower part as lower part in the drawings for convenience, the upper part may be named lower part and the lower part may be named upper part without departing from the scope of right of the present invention .

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as the present invention is generally understood by those skilled in the art. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the meaning in the context of the relevant art and are to be construed as ideal or overly formal in meaning unless explicitly defined in the present application Do not.

1 is a process flowchart illustrating a method of manufacturing a semiconductor device in accordance with embodiments of the inventive concept.

Referring to FIG. 1, a structure may be formed on a semiconductor substrate. The semiconductor substrate may be a silicon substrate. The structure may be a structure having a vertical side. A semiconductor substrate may be loaded into the process chamber. (S5) A deposition film may be formed on the semiconductor substrate by supplying a process material including a film-control material and a precursor material into the process chamber in which the semiconductor substrate is located. The deposition film may include an insulating material film, a semiconductor material film, or a conductive material film. Forming the deposition film may include repeatedly forming a unit layer until a deposition film having a desired thickness is formed.

The semiconductor substrate on which the deposition film is formed may be unloaded from the process chamber. A semiconductor chip may be formed using the unloaded semiconductor substrate. The semiconductor chip may be a non-memory semiconductor chip or a memory semiconductor chip. The semiconductor component may be manufactured using the semiconductor chip. (S25) An electronic product can be manufactured using the semiconductor component. (S30)

The semiconductor apparatus for performing a step (S10) of forming a deposition film on a semiconductor substrate by supplying the process material including the film-control material and the precursor material into the process chamber includes an atomic layer deposition (ALD). Or it may be a facility that can perform a chemical vapor deposition (CVD) process. The semiconductor facility may include the process chamber. The process chamber may be a chamber in which a semiconductor substrate on which the structure is formed is loaded to perform an atomic layer deposition (ALD) or chemical vapor deposition (CVD) process. A process material supply system may be provided for supplying the film-controlled material and the precursor material into the process chamber. A semiconductor device including such a process chamber and a process material supply system will be described with reference to FIG. 2. 2 is a view conceptually illustrating a facility for manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 2, the semiconductor facility 1a may include a process material supply system 20a capable of independently supplying the film-control material 14 and the precursor material 16 into the process chamber 10. The process material supply system 20a supplies the precursor material 16 and the film-control material 14 into the process chamber 10 independently of each other and at different times, or the precursor material 16 And the film-control material 14 may be simultaneously supplied into the process chamber 10. The process chamber 10 may be a chamber in which the semiconductor substrate 100 on which the structure is formed may be loaded / unloaded.

In one example, the membrane-controlling material 14 may be a ligand-hydrogen compound, which may be represented by "LH", and the precursor material 16 may be represented by "ML _n ". In the "ML _n ", "M" may be a central atom of the precursor material 16, "L" may be a ligand bonded to the central atom "M" of the precursor material 16, " n "is a number determined by the central atom" M "and the ligand" L ", for example, may be any value between 2 and 6. The film-control material 14 may be a hydrogen compound of the ligand “L” of the precursor material 16. For example, when the precursor material 16 is a zirconium precursor represented by the formula “Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ ”, the film-control material 14 is a ligand of the zirconium precursor. Hydrogen compound (HN (CH ₃ ) (CH ₂ CH ₃ )) of (N (CH ₃ ) (CH ₂ CH ₃ )). When the precursor material 16 is a ruthenium precursor represented by the formula “Ru (EtCp) ₂ ”, the film-controlling material 14 may be a hydrogen compound (HEtCp) of the ligand (EtCp) of the ruthenium precursor. When the precursor material 16 is a titanium precursor represented by the formula "Ti (NMe ₂ ) ₄ ", the film-controlling material 14 may be a hydrogen compound (HNMe ₂ ) of the ligand (NMe ₂ ) of the titanium precursor. have. Here, "Me" may be a methyl group (CH ₃ ).

In another example, the precursor material 16 may be represented by M (L ^a ) _n (L ^b ) _m and the film-controlled material 14 may be represented by L ^a H or L ^b H. In M (L ^a ) _n (L ^b ) _m , “M” may be a central atom of the precursor material 16 and “L ^a ” may be a first ligand that binds to the central atom (M) And “L ^b ” may be a second ligand which binds to the central atom (M) and is different from the first ligand. "n" may be a number determined by the central atom (M) and the first ligand (L ^a ), "m" may be a number determined by the center atom (M) and the second ligand (L ^b ).

The film-control material 14 is a hydrogen compound L ^a H of the first ligand L ^a of the precursor material 16, or ^a hydrogen compound L of the second ligand L ^b of the precursor material 16. ^b H. For example, the precursor material 16 may be CpZr (N (CH ₃ ) ₂ ) ₃ , and the membrane-controlling material 14 may be a hydride of a ligand of CpZr (N (CH ₃ ) ₂ ) ₃ . Can be. Here, "Cp" may be a cyclopentadienyl group. The membrane-controlling material 14 may be a hydride dimethylamine of ligand N (CH ₃ ) ₂ bonded with the central atom Zr of precursor CpZr (N (CH ₃ ) ₂ ) ₃ . Here, dimethylamine may be HN (CH ₃ ) ₂ .

In another example, the precursor material 16 may be M (L ^a ) _n (L ^b ) _m , and the film-control material 14 may be L ^c H. In this case, L ^c H of the film-control material 14 may be a material capable of forming M (L ^c ) _x (L ^d ) _y in combination with the central atom “M” of the precursor material 16. . Here, in M (L ^c ) _x (L ^d ) _y , the ligand L ^d may be either the first ligand L ^a or the second ligand L ^b of the precursor material 16. In addition, M (L ^c ) _x (L ^d ) _y may be a material usable in a process for forming the deposition film by replacing the precursor material 16. Where "n" is the binding state between the central atom "M" and the ligand "L ^a ", "m" is the binding state between the central atom "M" and the ligand "L ^b ", and "x" is the central atom "M The binding state between "and ligand" L ^c "," y "may be a number determined by the binding state between central atom" M "and ligand" L ^d ". For example, when the precursor material 16 is a TEMAZ precursor, the film-controlling material 14 may be dimethylamine. The TEMAZ may be of formula Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ , and the dimethylamine may be of formula HN (CH ₃ ) ₂ . When the precursor material 16 is a CpZr (N (CH ₃ ) ₂ ) ₃ precursor, the film-controlling material 14 may be "Ethylmethylamine". Here, the Ethylmethylamine may be a chemical formula HN (CH ₃ ) (CH ₂ CH ₃ ).

In another example, the precursor material 16 may be M (L ^a ) _n (L ^b ) _m , and the film-control material 14 may be an alkyl compound of a ligand of the precursor material 16. . For example, the membrane control material 14 may be L ^a R or L ^b R. Here, L ^a and L ^b may be ligands bonded to the central atom M of the precursor, and R may be an alkyl compound or an alkyl compound such as CH ₃ or CH ₂ CH ₃ . For example, the precursor material 16 may be TEMAZ or CpZr (N (CH ₃ ) ₂ ) ₃ , the film-controlling material 14 may be NMe ₃ or NEt ₃ , or the like. "Me" may refer to a methyl group, "Et" may refer to an ethyl group, and N may be nitrogen.

In another example, the precursor material 16 may be M (L ^a ) _n (L ^b ) _m and the film-control material 14 may be L ^c R. The L ^c R may be a material capable of combining with the central atom M of the precursor material 16 to form a different precursor (eg, M (L ^c ) _x (L ^d ) _y ) from the precursor material 16. have. In the L ^c R, Lc may be a compound capable of forming a precursor different from the precursor material 16, such as M (L ^c ) _x (L ^d ) _y, etc., R is CH ₃ or CH ₂ CH ₃ It may be the same alkyl compound or alkyl-based compound. Here, precursor M (L ^c ) _x (L ^d ) _{y different} from precursor material 16 may be a material available to replace the precursor material 16 to form the deposition film.

The technical spirit of the present invention is not limited to the zirconium precursor, the titanium precursor, or the ruthetium precursor. For example, as the titanium precursor, not only a precursor represented by the above-described formula Ti (NMe ₂ ) ₄ , but a material such as tetrakis (dimethylamido) titanim (TDMAT) may be used. In another example, when the film-controlling material 14 is a material represented by the chemical formula of "L ^a H", and the precursor material 16 is a precursor represented by the chemical formula of "ML ^b _n ", the precursor material In the formula "ML ^b _n ", the central atom "M" represents Be, B, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, It may include any one or more of Pb or Bi. In addition, the ligand "L ^b " of the precursor material 16 or the ligand "L ^a " of the membrane-controlling material 14 is independently H, F, Cl, Br, I, C1-10 alkyl, C1- C9 alkoxy, C5-C12 aryl, b-diketonate, cyclopentadienyl, C1-C8 alkylcyclopentadienyl, C1-C9 amino, C1-C9 thio or amidinate, or H, F, Cl, Br, I, C1-10 alkyl It may be a derivative in which halogen is added to any one of C1-C9 alkoxy, C5-C12 aryl, b-diketonate, cyclopentadienyl, C1-C8 alkylcyclopentadienyl, C1-C9 amino, C1-C9 thio or amidinate. Alternatively, the ligand "L ^b " of the precursor material 16 or ligand "L ^a " of the membrane-controlling material 14 is independently C1-C10 ether, C1-C12 amine, C1-C10 sulfide, C1- It may be any one of C9 nitrile, pyridine, pyrrole or furan, or a derivative in which halogen is added to any of C1-C10 ether, C1-C12 amine, C1-C10 sulfide, C1-C9 nitrile, pyridine, pyrrole or furan. .

The process material supply system 20a may include a precursor supply device 30a and a film-controlled material supply device 60a. The precursor supply device 30a may be a device for supplying the precursor material 16 into the process chamber 10.

The precursor supply device 30a may include a precursor storage container 40 and a vaporizer 50. The precursor storage container 40 and the vaporizer 50 may be connected by a pipe 42, the flow rate control device 44 may be disposed in the pipe 42. The vaporizer 50 and the process chamber 10 may be connected by a pipe 52, and a flow control device 54 may be disposed in the pipe 52.

The precursor material 16 in the precursor storage container 40 may be transferred to the vaporizer 50 and vaporized in the vaporizer 50. In addition, the precursor material vaporized in the vaporizer 50 may be supplied into the process chamber 10.

The membrane-controlled material supply device 60a may be a device for supplying the membrane-controlled material 14 into the process chamber 10. The membrane-controlled material 14 may be stored in the membrane-controlled material supply device 60a, and the membrane-controlled material 14 is transferred from the membrane-controlled material supply device 60a to the process chamber 10. ) May be supplied through the pipe 62.

 The membrane-controlled material supply device 60a and the process chamber 10 may be connected by the pipe 62, and may control the flow rate of the membrane-controlled material 14 in the pipe 62. Flow control device 64 may be disposed. The pipes 42, 52, and 62 may be pipes through which fluid can flow, and the flow control devices 44, 54, and 64 may include a valve system capable of controlling the flow of the fluid.

The process material supply system 20a may be a system capable of supplying the precursor material 16 and the film-control material 14 independently into the process chamber 10. The process material supply system 20a0 may supply the precursor material 16 and the film-control material 14 into the process chamber 10 at different times.

Semiconductor manufacturing equipment for manufacturing a semiconductor device according to an embodiment of the present invention is not limited to the equipment described in FIG. Other examples of equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIGS. 3 to 6, respectively. 3 to 6 are diagrams conceptually showing other examples of equipment for manufacturing a semiconductor device according to an embodiment of the inventive concept.

3 is a view conceptually illustrating another example of a facility for manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 3, a semiconductor facility 1b may be provided that includes a process material supply system 20b capable of supplying a precursor material 16 and a film-controlled material 14 into the process chamber 10. The process material supply system 20b supplies a precursor supply device 30b for supplying the precursor material 16 into the process chamber 10 and the film-controlled material 14 into the process chamber 10. And a membrane-controlled material supply device 60b for the purpose of.

The precursor supply device 30b may include a precursor storage container 40 capable of storing the precursor material 16 in a liquid state and a vaporizer 50 capable of vaporizing the precursor material 16. The precursor storage container 40 and the vaporizer 50 may be connected by a pipe 42, the flow rate control device 44 may be disposed in the pipe 42. The vaporizer 50 and the process chamber 10 may be connected by a pipe 52.

The pipe connecting the vaporizer 50 and the process chamber 10 may be defined as a first pipe 52. The membrane-controlled material supply device 60b may be connected to the first pipe 52. The membrane-controlled material supply device 60b may be provided with a second pipe 62 connecting the first pipe 52 and the membrane-controlled material supply device 60b.

The flow rate control device 54 may be disposed in the first pipe 52 between the connecting portion 56 of the first pipe 52 and the second pipe 62 and the vaporizer 50. The flow rate control device 58 may be disposed in the first pipe 52 between the connection portion 56 of the first pipe 52 and the second pipe 62 and the process chamber 50.

The membrane-controlled material 14 may be stored in the membrane-controlled material supply device 60b, and the membrane-controlled material 14 is transferred from the membrane-controlled material supply device 60b to the second pipe 62. And the first pipe 52 may be supplied into the process chamber 10.

The process material supply system 20b may supply the precursor material 16 and the film-control material 14 into the process chamber 10 at different times. In addition, the process material supply system 20b may simultaneously supply the precursor material 16 and the film-controlled material 14. In the case where the precursor material 16 and the film-controlled material 14 are simultaneously supplied into the process chamber 10, the process material supply system 20b causes the film-controlled material 14 to be supplied to the vaporizer. 50 may be mixed with the precursor material in a vaporized state and supplied into the process chamber 10.

4 is a view conceptually illustrating another example of a facility for manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 4, a semiconductor installation 1c may be provided that includes a process material supply system 20c capable of supplying a precursor material 16 and a film-controlled material 14 into the process chamber 10.

The process material supply system 20c may include a precursor supply device 30c and a film-controlled material supply device 60c.

The precursor supply device 30c may include a precursor storage container 40 capable of storing the precursor material 16 in a liquid state and a vaporizer 50 capable of vaporizing the precursor material 16. The precursor storage container 40 and the vaporizer 50 may be connected by a pipe 42. The vaporizer 50 and the process chamber 10 may be connected by a pipe 52, and a flow control device 54 may be disposed in the pipe 52.

A pipe connecting the precursor storage container 40 and the vaporizer 50 may be defined as a first pipe 42. The membrane-controlled material supply device 60c capable of storing the membrane-controlled material 14 may be connected to the first pipe 42 through a second pipe 62. Accordingly, the second pipe 62 may connect the first pipe 42 and the membrane-controlled material supply device 30c. A flow control device 64 capable of controlling the flow rate of the membrane-controlled material 14 may be disposed in the second pipe 62.

A flow rate control device 44 may be provided between the connecting portion 46 of the first pipe 42 and the second pipe 62 and the precursor storage container 40, and the first pipe 42 may be provided. ) And a flow control device 48 may be provided between the connecting portion 46 of the second pipe 62 and the first vaporizer 50. The membrane-controlled material 14 in the membrane-controlled material supply device 60c may be supplied into the process chamber 10 through the vaporizer 50.

The process material supply system 20c may supply the precursor material 16 and the film-control material 14 into the process chamber 10 independently of each other. The process material supply system 20c may also supply the precursor material 16 and the film-controlled material 14 simultaneously.

In the case where the precursor material 16 and the film-control material 14 are simultaneously supplied into the process chamber 10, the precursor material 16 and the film-control material 14 are the vaporizer 50. Simultaneously moved into and vaporized at the same time in the vaporizer 50 may be supplied into the process chamber 10.

5 is a view conceptually illustrating another example of a facility for manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 5, a semiconductor installation 1d may be provided that includes a process material supply system 20d capable of supplying a precursor material 16 and a film-controlled material 14 into the process chamber 10. The process material supply system 20d may include a precursor supply device 30d and a film-controlled material supply device 60d.

The precursor supply device 30c may include a precursor storage container 40 capable of storing the precursor material 16 in a liquid state and a vaporizer 50 capable of vaporizing the precursor material 16. The precursor storage container 40 and the vaporizer 50 may be connected by a pipe 42. The vaporizer 50 and the process chamber 10 may be connected by a pipe 52, and a flow control device 54 may be disposed in the pipe 52.

The membrane-controlled substance supply device 60d may store the membrane-controlled substance 14. The film-controlled material supply device 60d may be connected to the precursor supply device 30d through a pipe 62. The flow rate control device 64 may be disposed in the pipe 62.

The film-controlled material supply device 60d may be connected to the precursor storage container 40 of the precursor supply device 30d through the pipe 62.

The film-controlled material 14 in the film-controlled material supply device 60d moves into the precursor storage container 40 and is mixed with the precursor material 16 and then from the precursor storage container 40. The vaporizer 50 may be supplied into the process chamber 10 together with the precursor material 16.

6 is a view conceptually illustrating another example of a facility for manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 6, a semiconductor facility 1e may be provided that includes a process material supply system 20e capable of supplying a precursor material 16 and a film-controlled material 14 into the process chamber 10.

The process material supply system 20e may include a process material storage container 70 and a vaporizer 50. The process material storage container 70 may store the precursor material and the film-controlled material simultaneously. For example, the precursor material and the film-controlled material may be stored in the process material storage container 70 as a mixed liquid material 18.

The process material storage container 70 may be connected to the vaporizer 50 and the pipe 72. The fluid control device 74 may be disposed in the pipe 72. The vaporizer 50 may be connected to the process chamber 10 and the pipe 52. The fluid control device 54 may be disposed in the pipe 52.

Thus, the process material 18 including the precursor material and the film-controlled material in the process material storage container 70 may be transferred to the vaporizer 50 and vaporized in the vaporizer 50. The precursor material and the film-controlled material vaporized in the vaporizer 50 may be simultaneously supplied into the process chamber 10.

As described with reference to FIGS. 1 and 2-6, according to embodiments of the inventive concept, the supply of the film-control material 14 and the precursor material 16 into the process chamber 10 may be performed. Can be used to form a deposited film on a semiconductor substrate. As such, the method or order of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 will be described with reference to FIGS. 7A to 7I, respectively.

7A is a gas pulsing diagram for explaining an example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any one of FIGS. 2 to 4 and FIG. 7A, after the film-control material 14 is supplied to the process chamber 10 before the precursor material 16, the film- The supply of control material 14 can be stopped and the precursor material 16 can be supplied.

7B is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any one of FIGS. 2 to 4 and FIG. 7B, the film-controlled material 14 is started into the process chamber 10 before the precursor material 16 and the film is started. The supply of the precursor material 16 can be started while the control material 14 is being supplied and the supply of the precursor material 16 can be stopped after the supply of the film-control material 14 is stopped. . Thus, the film-control material 14 and the precursor material 16 may be supplied together in the process chamber 10 for a period of time.

7C is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any one of FIGS. 2 to 4 and FIG. 7C, after the precursor material 16 is supplied to the process chamber 10 before the film-control material 14, the precursor material Supply of the membrane-controlled material 14 can be stopped and supply of 16.

FIG. 7D is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the installation of any one of FIGS. 2-4, and FIG. 7D, the precursor material 16 is started into the process chamber 10 before the film-controlled material 14 and the precursor material is started. The supply of the film-control material 14 can be stopped while the supply of the film-control material 14 is started while the supply of the precursor material 16 is stopped while the 16 is being supplied. Thus, the film-control material 14 and the precursor material 16 may be supplied together in the process chamber 10 for a period of time.

FIG. 7E is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any one of FIGS. 2 to 6 and FIG. 7E, simultaneously supplying and simultaneously supplying the precursor material 16 and the film-controlled material 14 into the process chamber 10. You can stop.

FIG. 7F is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any one of FIGS. 2 to 4 and FIG. 7F, the film-controlled material 14 is supplied into the process chamber 10 before the precursor material 16 and the film-controlled. The precursor material 16 may be supplied together with the film-control material 14 in the middle of the material 14 being supplied. Subsequently, the supply of the precursor material 16 and the film-control material 14 into the process chamber 10 may be stopped at the same time.

7G is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any of FIGS. 2-4 and FIG. 7G, the film-controlled material is supplied to supply the precursor material 16 and the film-controlled material 14 into the process chamber 10. After first pulsing the material 14, the precursor material 16 may be pulsed, followed by the second pulsing of the film-control material 14. Supplying the film-control material 14 into the process chamber 10 before the precursor material 16, stopping the supply of the film-control material 14 and supplying the precursor material 16, The film-control material 14 may be supplied while the supply of the precursor material 16 is stopped.

7H is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any one of FIGS. 2-4 and FIG. 7H, the film-controlled material is supplied to supply the precursor material 16 and the film-controlled material 14 into the process chamber 10. The precursor material 16 may be pulsed in the middle of pulsing the material 14. The precursor material 16 may be supplied in the middle of supplying the film-controlled material 14 into the process chamber 10. Supplying the film-control material 14 into the process chamber 10 before the precursor material 16, and after a predetermined time, supplying the precursor material 16 with the film-control material 14, The film-controlling material may be supplied even after the supply of the precursor material 16 is stopped.

FIG. 7I is a gas pulsing diagram for explaining another example of a method of supplying the film-control material 14 and the precursor material 16 into the process chamber 10 in the process chamber 10. Referring to the semiconductor device of any one of FIGS. 2 to 4 and FIG. 7I, the film-control material 14 and the precursor material 16 are simultaneously supplied into the process chamber 10, and the film-control is performed. Material 14 may be supplied for a longer time than precursor material 16.

FIG. 8 is a diagram conceptually illustrating another example of a semiconductor facility for manufacturing a semiconductor device according to example embodiments of the inventive concepts; FIG.

Referring to FIG. 8, a semiconductor device 1 including a process chamber 10, a first process material supply device 20, and a second process material supply device 80 may be provided. The semiconductor facility 1 may be a deposition facility such as ALD or CVD. The semiconductor substrate 100 having the structure formed therein may be loaded in the process chamber 10.

The first process material supply device 20 may be a device for supplying a first process material into the process chamber 10. For example, the first process material supply device 20 may be a device for supplying a first precursor and a first film-controlled material into the process chamber 10. The first process material supply device 20 may be any one of the process material supply systems 20a, 20b, 20c, 20d, and 20e described with reference to FIGS. 2 to 6. For example, the first process material supply device 20 may supply the film-controlled material 14 and the precursor material 16 as described in FIGS. 2 to 6 into the process chamber 10. It may be a device.

The second process material supply device 80 may be a device for supplying a second process material into the process chamber 10.

In embodiments, the second process material supply device 80 may include a second process material including a second precursor material having a second center atom different from the first center atom of the first precursor material. 10) may be a device for supplying. The second process material supply device 80 may be a device for supplying a second film-controlled material into the process chamber 10 together with the second precursor material. The second process material supply device 80 may be any one of the process material supply systems 20a, 20b, 20c, 20d, and 20e described with reference to FIGS. 2 to 6.

In example embodiments, the second process material supply device 80 may be supplied from the first process material supply device 20 into the process chamber 10 and adsorbed onto the surface of the semiconductor substrate 100. It may be a device for supplying a reactant that can react with the central atom of the material. For example, the central atom of the first precursor material supplied from the first process material supply device 10 into the process chamber 10 may be a metal, and in the second process material supply device 80, The reactant supplied into the process chamber 10 may be a material such as an oxidizing agent or a nitriding agent. The oxidant may include ozone (O ₃ ), oxygen (O ₂ ), water vapor (H ₂ O), ozone plasma or oxygen plasma. The nitriding agent may comprise ammonia (NH ₃ ), nitrogen dioxide (NO ₂ ) or nitrogen oxide (N ₂ O).

Accordingly, the metal atom of the first precursor material and the oxidant react to form a metal oxide on the semiconductor substrate 100 in the process chamber 10, or the metal atom of the first precursor and the nitriding agent react. Thus, metal nitride may be formed on the semiconductor substrate 100 in the process chamber 10.

FIG. 9 is a flowchart illustrating a step S10 of forming the deposition film described with reference to FIG. 1 in a method of manufacturing a semiconductor device according to an embodiment of the inventive concept. A method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIG. 9 along with FIGS. 1 and 8.

1, 8, and 9, a first process material including a film-controlling material and a precursor material is supplied into the process chamber 10 of the semiconductor facility 1 to be disposed on the semiconductor substrate 100. Can form a preliminary unit layer. The first process material may be supplied into the process chamber 10 through the pipe 22 from the first process material supply device 20 of the semiconductor device 1. The first process material supply device 20 may be any one of the process material supply systems 20a, 20b, 20c, 20d, and 20e described with reference to FIGS. 2 to 6.

The film-controlled material and the precursor may be formed by any one of the methods of supplying the film-controlled material 14 and the precursor material 16 into the process chamber 10 described with reference to FIGS. 7A-7I. It may be supplied in the process chamber 10. The process chamber 10 in which the semiconductor substrate having the preliminary unit layer is formed may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The second process material may be supplied into the process chamber 10 through the pipe 82 from the second process material supply device 80 of the semiconductor facility 1. The process chamber 10 in which the semiconductor substrate having the unit layer is formed may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer in one cycle may be repeatedly performed. When the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed may be unloaded from the process chamber 10.

1 and 8, an example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIGS. 10 to 21.

FIG. 10 is a gas pulsing diagram illustrating an example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept, and FIG. 11 is a method of manufacturing a semiconductor device according to an embodiment of the inventive concept. 12 to 21 are diagrams showing examples of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept. 12 to 21, FIGS. 12, 13, 17, 19, and 21 are cross-sectional views illustrating examples of a method of manufacturing a semiconductor device in accordance with some example embodiments of the inventive concepts. 14A and 14B are enlarged views of a portion indicated by “A” in FIG. 13 to illustrate an example of a method for forming a surface-control layer, and FIG. 15 is a diagram of a method for forming a surface-control layer. FIG. 13 is an enlarged view of portion “A” of FIG. 13 for explaining another example, and FIG. 16 is a diagram for describing another example of a method for forming a surface-control layer. 18A and 18B are enlarged views of a portion indicated by "A" in FIG. 17, and FIG. 20 is an enlarged view of a portion denoted by "A" in FIG. 19.

First, referring to FIGS. 1 and 12, the semiconductor substrate 100 may be prepared. The semiconductor substrate 100 may be a silicon substrate or a silicon wafer. An underlayer 105 may be formed on the semiconductor substrate 100.

The structure 110 may be formed on the semiconductor substrate 100 having the underlayer 105. (S1) The structure 110 may have a side surface 110s having a vertical portion. The side surface 110s of the structure 110 may be vertical. The side surface 110s of the structure 110 may include an upper side portion 110s1 and a lower side portion 110s2 disposed below the upper side portion 110s1. An opening 110a penetrating the structure 110 may be formed. The opening 110a may be defined by the side surfaces 110s of the structure 110. The opening 110a may have a depth D greater than the width W.

1, 8, and 12, the semiconductor substrate 100 having the structure 110 may be loaded into the process chamber 10 of the semiconductor facility 1. (S5)

1, 8, 10, 11, and 13, the film-control material 115 is supplied into the process chamber 10 in which the semiconductor substrate having the structure 110 is located. Surface-control layer 120 may be formed on a semiconductor substrate having 110. (S205)

The film-controlled material 115 may be supplied into the process chamber 10 from the first process material supply device 20. The first process material supply device 20 may be a process material supply system of any one of the process material supply systems 20a, 20b, and 20c described with reference to FIGS. 2, 3, and 4. Thus, the film-controlled material 115 is the same as the film-controlled material 14 supplied from any of the process material supply systems 20a, 20b, 20c described in FIGS. 2, 3, and 4. It may be a substance. Since the kind of the film-controlling materials 14 and 115 is described in the description of FIG. 2, detailed descriptions thereof will be omitted herein in order to avoid repeated descriptions.

The film-control material 115 may be supplied into the process chamber 10 with an inert gas such as argon. This inert gas may serve to move the membrane-controlled material 115 from the membrane-controlled material supply device into the process chamber 10.

An example of a method of forming the surface-control layer 120 will be described with reference to FIGS. 14A and 14B along with FIG. 8. 14A and 14B are enlarged views of a portion indicated by “A” in FIG. 13.

8, 13, and 14A, the film-control material 115 may be supplied into the process chamber 10 in which the semiconductor substrate having the structure 110 is located. The film-control material 115 may be the same material as the film-control material 14 described with reference to FIG. 2. For example, the membrane-controlling material 115 may be a ligand-hydrogen compound, which may be represented by any one of the examples of the membrane-controlling material 14 described in FIG. 2, eg, “L ^a -H”. have. Here, “L ^a ” may be a ligand that may be bonded to a central atom of a precursor for forming a deposited film, and “H” may be hydrogen.

8, 13, and 14B, the film-control material 115 supplied into the process chamber 10 is formed by the L ^a -of the ligand-hydrogen compound on the semiconductor substrate having the structure 110. Adsorbed in the H molecular state to form the first surface-control layer 120a. The first surface-control layer 120a may be formed by adsorbing the film-control material 115 on the surface of the semiconductor substrate having the structure 110 in the state of a ^La- H molecule. The film-control material 115a which does not form the surface-control layer 120a may remain in the empty space of the process chamber 10 in which the semiconductor substrate having the first surface-control layer 120a is located. have.

Another example of a method of forming the surface-control layer 120 will be referred to FIG. 15.

Referring to FIG. 15, the film-controlling material 115 may be supplied into the process chamber 10 with a ligand (L ¹ ) -hydrogen (H) compound, which may be represented as “L ¹ -H”. The ligand (L ¹ ) of the film-control material 115 may be bonded to a surface of the semiconductor substrate having the structure 110 to form a second surface-control layer 120b. The membrane-hydrogen (H) of the control material (115) is the film - as bonded to the surface of the ligand (L ¹⁾ of the control material 115, the structure 110 can be chipped away from the ligand (L ¹⁾ . Accordingly, the second surface-control layer 120b may be formed of the ligand L ¹ of the film-control material 115.

Another example of a method of forming the surface-control layer 120 will be referred to FIG. 16. 16 illustrates a portion of the surface of the structure 110 and the surface-control layer 120.

Referring to FIG. 16, the film-controlling material 115 may be supplied into the process chamber 10 with a ligand (L ² ) -hydrogen (H) compound, which may be represented as “L ² -H”. The film-control material 115 may be chemically adsorbed on the surface of the semiconductor substrate having the structure 110 to form the third surface-control layer 120. For example, the surface of the structure 110 may be formed by combining a first atom Ea and a second atom Eb. In addition, the ligand (L ² ) of the membrane control material 115 chemically bonds with the first atom (Ea) of the structure 110, and hydrogen (H) of the membrane control material 115 is The third surface-control layer 120 may be combined with the second atom Eb of the structure 110. For example, the membrane and physically coupled to the first atom (Ea) in which the ligand (L ²⁾ of hydrogen (H) compounds wherein the structure (110) - ligand (L ²⁾ of the control substance 115 ligand (L ²⁾ - a combination of hydrogen (H) ligand (L ²⁾ and hydrogen (H) of the compound can be cut off. In the ligand (L ² ) -hydrogen (H) compound, the hydrogen (H), which is in a molecular bond with the ligand (L ² ), may be bonded to the second atom (Eb).

When the surface of the structure 110 is a metal oxide, the first atom Ea may be a metal atom, and the second atom Eb may be an oxygen atom. In the ligand (L ² ) -hydrogen (H) compound of the membrane-controlling material 115, the ligand (L ² ) is disconnected from the hydrogen (H) and thus the first atom (Ea), that is, a metal atom Chemically bonded to, and the hydrogen (H) is disconnected from the ligand (L ² ) may be bonded to the second atom (Eb), that is, the oxygen atom.

When the surface of the structure 100 is a metal-nitride, the first atom Ea may be a metal atom such as titanium, and the second atom Eb may be nitrogen. For example, in the ligand (L ² ) -hydrogen (H) compound of the membrane-controlling material 115, the ligand (L ² ) is disconnected from the hydrogen (H) and the first atom (Ea) That is, the hydrogen (H) that is chemically bonded to a metal atom, and the bond (L ² ) is broken, may be bonded to the second atom (Eb), that is, a nitrogen atom.

In the first to third surface-control layers 120a, 120b, and 120c, the terms “first, second, and third” are various examples of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept. It is intended to describe the surface-control layer 120, which may be formed according to, and is not intended to limit the invention. For example, the surface-control layer 120 may be formed of any one of the first to third surface-control layers 120a, 120b, and 120c in FIGS. 14B, 15, and 16.

1, 8, 10, 11, and 17, a first precursor material 125 in the process chamber 10 in which the semiconductor substrate 100 having the surface-control layer 120 is located. The precursor adsorption layer 130 may be formed on the semiconductor substrate 100 having the surface-control layer 120. (S207)

The first precursor material 125 may be supplied into the process chamber 10 with an inert gas such as argon. This inert gas may serve to move the first precursor material 125 from the precursor supply device into the process chamber 10.

The first precursor material 125 may be supplied into the process chamber 10 from the first process material supply device 20. The first process material supply device 20 may be a process material supply system of any one of the process material supply systems 20a, 20b, and 20c described with reference to FIGS. 2, 3, and 4. Thus, the first precursor material 125 may be the same material as the precursor material 16 supplied from any of the process material supply systems 20a, 20b, 20c described in FIGS. 2, 3, and 4. Can be. Since the types of the precursors 16 and 125 are described in the description of FIG. 2, detailed descriptions thereof will be omitted herein to avoid repeated descriptions.

The precursor adsorption layer 130 may be formed by physically adsorbing the first precursor material 125 to the surface-control layer 120. The precursor adsorption layer 130 may be physically adsorbed (or coupled) on the surface-control layer 120.

The surface-control layer 120 and the precursor adsorption layer 130 may constitute a preliminary unit layer 135. Therefore, the preliminary unit layer 135 may be formed by supplying a first process material including the film-control material 115 and the first precursor material 125 into the process chamber 10. (S210) The preliminary unit layer 135 includes the surface-control layer 120 and the portion "B '", which is an enlarged view of the portion labeled "B" with the preliminary unit layer 135 in FIG. 17. The precursor adsorption layer 130 may be physically coupled onto the surface-control layer 120.

An example of a method of forming the precursor adsorption layer 130 will be described with reference to FIGS. 18A and 18B along with FIG. 8. 18A and 18B are enlarged views of a portion denoted by "A" in FIG. 17.

8, 17, and 18A, a first precursor material 125 may be supplied into the process chamber 10 in which the semiconductor substrate 100 having the surface-control layer 120 is located. The first precursor material 125 may be supplied after stopping the supply of the film-control material 115 into the process chamber 10.

The first precursor material 125 may be the same material as the precursor material 16 described with reference to FIG. 2. For example, the first precursor material 125 may be any one of the examples of the precursor material 16 described with reference to FIG. 2, for example, “ML ^b _n ”. Here, "M" may be a central atom of the first precursor material 125 and "L ^b " may be a ligand bonded to the central atom "M".

The film-control material 115 and the first precursor material 125 may be formed of the same material as the film-control material 14 and the precursor material 16 described in FIG. Will be omitted.

8, 17, and 18B, the first precursor material 125 supplied into the process chamber 10 is adsorbed onto the surface of the surface-control layer 120 to form the precursor adsorption layer 130. Can be formed. The surface-control layer 120 may be formed on the surface of the structure 110 to prevent the first precursor material 125 from being chemically adsorbed on the surface of the structure 110. The first precursor material 125 may be physically adsorbed to the surface-control layer 120.

In some embodiments, the surface-control layer 120 may be any one of the first to third surface-control layers 120a, 120b, 120c described with reference to FIGS. 14B, 15, and 16.

Meanwhile, a portion 125a of the first precursor material 125 supplied in the process chamber 10 may remain in the empty space in the process chamber without being adsorbed to the surface-control layer 120. In addition, a portion 115a of the film-control material 115 may also remain together with the first precursor 125a in the empty space of the process chamber 10. Thus, a first process material including the film-control material 115 and the first precursor material 125 is supplied into the process chamber 10 to provide the surface-control layer 120 and the precursor adsorption layer ( A preliminary unit layer 135 including 130 may be formed. (S210)

While the first precursor material 125 is supplied into the process chamber 10, the film-controlled material 115a remaining in the process chamber 10 may be bonded to the first adsorbed first precursor and / or intermolecularly. The compound 127 may be formed by combining with the first precursor. For example, when the molecules of the first precursor material 125 supplied in the process chamber 10 form clusters with weak coordination bonds, the film remaining in the process chamber 10. The control material 115a breaks the bond between the molecules of the weakly coordinated first precursor material 125 and makes strong coordination with the molecules of the first precursor material 125. Here, in "weak coordination bond" and "strong coordination bond", "weak" and "strong" are terms used to describe the relative coordination bond relationship. For example, the coordination bond between the first precursor material 125 and the film-control material 115a may mean that the coordination bond between the molecules of the first precursor material 125 is stronger than that of the coordination bond.

The compound 127 may be defined as a second precursor material capable of forming a deposited film. The compound, that is, the second precursor material 127 may be moved into the lower region of the opening 110a and adsorbed onto the surface of the substrate positioned in the lower region of the opening 110a. Accordingly, the preliminary unit in a process atmosphere in which the first precursor material 125, the second precursor material 127, and the remaining film-control material 115a coexist in the lower region of the opening 110a. Layer 135 may be formed.

1, 8, 10, 11, and 19, the process chamber 10 in which the semiconductor substrate 100 having the preliminary unit layer 135 is located may be purged. Subsequently, the second process material 140 may be supplied into the process chamber 10 to form a unit layer 145 on the semiconductor substrate 100 having the preliminary unit layer 135. (S220)

Forming the preliminary unit layer 135 into the unit layer 145 and forming the preliminary unit layer 135 and the ligand of the precursor adsorption layer 130 and the membrane of the surface-control layer 120. The control material may be separated from the preliminary unit layer 135 and formed as a reaction byproduct 147.

The second process material 140 may include an oxidizing agent, a nitriding agent, or a reducing agent. The oxidant may be an oxygen precursor, and the nitriding agent may be a nitrogen precursor. The second process material 140 may be an oxidant including ozone (O ₃ ), oxygen (O ₂ ), water vapor (H ₂ O), ozone plasma, or oxygen plasma. Alternatively, the second process material 140 may be a nitriding agent including ammonia (NH ₃ ), nitrogen dioxide (NO ₂ ) or nitrogen oxide (N ₂ O). In contrast, the second process material 140 may be formed of a metal precursor, such as tungsten precursor or ruthenium precursor, adsorbed on the surface of the semiconductor substrate, so that only metal atoms such as tungsten or ruthenium remain on the surface of the semiconductor substrate to form a tungsten layer or ruthenium layer. It may be a reducing agent that serves to remove the ligand bound to the metal atom to form.

When the second process material 140 is an oxidant such as ozone, the unit layer 145 may be an oxide in which oxygen and the central atom of the first precursor material 125 are bonded. For example, when the central atom of the first precursor material 125 is a metal such as zirconium, titanium or ruthenium, the unit layer 145 may be formed of a metal oxide such as zirconium oxide, titanium oxide or ruthenium oxide. have.

When the second process material 140 is a nitriding agent, the unit layer 145 may be a nitride in which the central atom of the first precursor material 125 and nitrogen are bonded. For example, when the central atom of the first precursor material 125 is a metal such as tungsten or titanium, the unit layer 145 may be formed of a metal nitride such as tungsten nitride or titanium nitride.

When the second process material 140 is a reducing agent, the unit layer 145 may be a metal layer made of a central atom of the first precursor material 125. For example, when the central atom of the first precursor material 125 is a metal such as tungsten, ruthenium or titanium, the unit layer 145 may be formed of a metal layer such as tungsten layer, ruthenium layer or titanium layer. have.

The preliminary unit layer 135 may be formed of the unit layer 145 by reacting with the second process material 140. The unit layer 145 may be formed of any one of an oxide, a nitride, or a metal material. In addition, the unit layer 145 may be a single metal layer, a binary metal oxide, or a binary metal nitride. In addition, the unit layer 145 may be a multi-component material layer including at least three elements. For example, when the second process material 140 is an oxidizing agent such as ozone, as shown in FIG. 20, the unit layer 145 may be an oxide which may be represented by MO _x . Here, "M" may be a central atom of the first precursor material 125, "O" may be an oxygen atom, and "x" may be an amount of one that may be determined according to the type of the central atom. Can be. For example, in the case of a metal oxide such as TiO ₂ , “x” may be two.

Referring to FIG. 21, the process chamber 10 may be purged to remove reaction by-products 147 generated while forming the unit layer 145. The reaction byproduct 147 may be removed while purging the process chamber 10. The unit layer 145 may be repeatedly formed to form a deposition film 150 having a desired thickness.

The first precursor material 125 and the film-control material 115 may be the same materials as the precursor material 16 and the film-control material 14 described with reference to FIG. 2. The kind of the first precursor material 125 and the film-control material 115 and the kind of the second process material 140 will be described by way of example.

<Example 1>

The first precursor material 125 may be a material represented by ML _n , and the film-control material 115 may be a material represented by LH. Here, in the ML _n , M may be a central atom, L may be a ligand that binds to the central atom M, n is a number determined by the central atom M and ligand L, for example between 2 to 6 It can be any one value of. In LH of the film-control material 115, L may be the same material as the ligand L of the first precursor material 125. Thus, the film-control material 125 may be a hydrogen compound of the ligand of the first precursor material 125.

As an example, the first precursor material 125 may be a TEMAZ precursor, and the film-controlling material 115 may be a hydride of a ligand constituting TEMAZ. Here, the chemical formula of TEMAZ may be Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ . In precursor Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ the central atom is Zr and the ligand is N (CH ₃ ) (CH ₂ CH ₃ ) Lt; / RTI &gt; The membrane-controlling material 115 is ligand N (CH ₃ ) (CH ₂ CH ₃ ) May be a hydrogen compound of "Ethylmethylamine". The chemical formula of Ethylmethylamine may be HN (CH ₃ ) (CH ₂ CH ₃ ).

As another example, the first precursor material 125 is Ru (EtCp) ₂ , and the film-control material 115 is a hydrogen compound of the ligand EtCp bonded to the central atom Ru of Ru (EtCp) ₂ , that is, HEtCpyl. Can be.

As another example, the first precursor material 125 is Ti (NMe ₂ ) ₄ , and the film-control material 115 is a hydrogen compound of ligand NMe ₂ bonded with the central atom Ti of Ti (NMe ₂ ) ₄ . That is, it may be HNMe ₂ .

<Example 2>

The first precursor material 125 may be a material that can be represented by the formula M (L ^a ) _n (L ^b ) _m , and the film-control material 115 is represented by L ^a H or L ^b H It may be a substance that can be represented. In M (L ^a ) _n (L ^b ) _m of the first precursor material 125, M may be a central atom of the precursor, L ^a may be a first ligand that binds to the central atom M, L ^b may be a second ligand which binds to the central atom M and is different from the first ligand. N may be a number determined by the central atom M and the first ligand L ^a , and m may be a number determined by the central atom M and the second ligand L ^b .

The film-control material 115 is a hydrogen compound L ^a H of the first ligand (L ^a ) of the first precursor material 125, or a second ligand (L ^b ) of the first precursor material 125. May be a hydrogen compound L ^b H. For example, the first precursor material 125 may be CpZr (N (CH ₃ ) ₂ ) ₃ , and the membrane-controlling material 115 may be a number of ligands of CpZr (N (CH ₃ ) ₂ ) ₃ . It may be a digest. Here, "Cp" may refer to a cyclopentadienyl group. The membrane-controlling material 115 may be a hydride dimethylamine of ligand N (CH ₃ ) ₂ bonded with the central atom Zr of precursor CpZr (N (CH ₃ ) ₂ ) ₃ . Here, dimethylamine may be HN (CH ₃ ) ₂ .

<Example 3>

The first precursor material 125 may be M (L ^a ) _n (L ^b ) _m , and the film-control material 115 may be L ^c H. In this case, the chemical formula L ^c H of the film control material 115 may be a material capable of forming M (L ^c ) _x (L ^d ) _y . Here, in the formula M (L ^c ) _x (L ^d ) _y , L ^d may be L ^a or L ^b . In addition, M (L ^c ) _x (L ^d ) _y may be a material usable in a process for forming the deposition film by replacing the first precursor material 125. Where "n" is the binding state between the central atom "M" and the ligand "L ^a ", "m" is the binding state between the central atom "M" and the ligand "L ^b ", and "x" is the central atom "M The binding state between "and ligand" L ^c "," y "may be an amount number determined by the binding state between central atom" M "and ligand" L ^d ".

The first precursor material 125 may be M (L ^a ) _n (L ^b ) _m , and the film-control material 115 is L ^c H as a first example, the first precursor material 125 May be TEMAZ and the membrane-controlling material 115 may be dimethylamine. The TEMAZ may be Zr [N (CH ₃ ) (CH ₂ CH ₃ )] ₄ , and the dimethylamine may be HN (CH ₃ ) ₂ .

The first precursor material 125 may be M (L ^a ) _n (L ^b ) _m , and the film-control material 115 is L ^c H, in a second example, the first precursor material 125 May be CpZr (N (CH ₃ ) ₂ ) ₃ and the membrane-controlling material 115 may be “ethylmethylamine”. The Ethylmethylamine may be HN (CH ₃ ) (CH ₂ CH ₃ ).

<Example 4>

The first precursor material 125 may be M (L ^a ) _n (L ^b ) _m , and the film-control material 115 may be an alkyl compound of a ligand of the first precursor material 125. For example, the membrane control material 115 may be L ^a- R or L ^b- R. Here, L ^a and L ^b may be ligands bonded to the central atom M of the precursor, and R may be an alkyl compound or an alkyl compound such as CH ₃ or CH ₂ CH ₃ .

For example, the first precursor material 125 may be TEMAZ or CpZr (N (CH ₃ ) ₂ ) ₃ , the film-controlling material 115 may be NMe _3, NEt ₃ , or the like. "Me" may refer to a methyl group and "Et" may refer to an ethyl group.

<Example 5>

The first precursor material 125 may be M (L ^a ) _n (L ^b ) _m and the film-control material 115 may be L ^c R. The L ^c R may combine with the central atom M of the first precursor material 125 to form a precursor different from the first precursor material 125 (eg, M (L ^c ) _x (L ^d ) _y ). Material may be present. In the L ^c R, Lc may be a compound capable of forming a precursor material different from the first precursor material 125, such as M (L ^c ) _x (L ^d ) _y , and R is CH ₃ or CH ₂ It may be an alkyl compound such as CH ₃ or an alkyl-based compound. Here, the precursor M (L ^c ) _x (L ^d ) _{y different} from the first precursor material 125 may be a material available to replace the first precursor material 125.

1 to 8, another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIGS. 22 to 29.

FIG. 22 is a gas pulsing diagram illustrating another example of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept, and FIG. 23 is another example of a method of manufacturing a semiconductor device, according to an embodiment of the inventive concept. 24 to 29 are diagrams illustrating another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.

24 to 29, FIGS. 24, 26, 28, and 29 are cross-sectional views illustrating another example of a method of fabricating a semiconductor device in accordance with some example embodiments of the inventive concepts, and FIGS. 25A and 25B illustrate the present invention. To illustrate another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept, FIGS. 24A and 27C are enlarged views, and FIGS. 27A to 27C illustrate one embodiment of the inventive concept. FIG. 26 is an enlarged view illustrating a portion “C” of FIG. 26 to describe another example of a method of manufacturing a semiconductor device.

First, referring to FIGS. 1, 8, 22, 23, and 24, as described with reference to FIG. 12, a base film 205 is formed on a semiconductor substrate 200, and the base film 205 is formed on the base film 205. The structures 210 may be formed in turn. (S1)

The structure 210 may have a side surface 210s including an upper side portion 210s1 and a lower side portion 210s2 below the upper side portion 210s1. The upper side portion 210s1 and the lower side portion 210s2 of the structure 210 may be vertical. An opening 210a penetrating the structure 110 may be formed. The opening 210a may be defined by the side surfaces 210s of the structure 210. The opening 210a may have a depth D greater than the width W.

A semiconductor substrate having the structure 210 may be loaded into the process chamber 10. (S5)

The first precursor material 215 is supplied into the process chamber 10 in which the semiconductor substrate 200 having the structure is located to form the superadsorption portion 220b on the semiconductor substrate 200 having the structure 210. The first preliminary unit layer 222 may be formed. The first preliminary unit layer 222 may be formed by adsorbing the first precursor material 215 on the surface of the semiconductor substrate having the structure 210.

The first preliminary unit layer 222 may be understood as a nonuniform preliminary unit layer. For example, the first preliminary unit layer 222 may include a first portion 221a including the superadsorbed portion 220b and a second portion 221b not including the superadsorbed portion. In the first preliminary unit layer 222, the first portion 221a may be thicker than the second portion 221b. Therefore, the first preliminary unit layer 222 may be formed of a layer having a non-uniform thickness.

The first portion 221a of the first preliminary unit layer 222 may include a base portion 220a and a superadsorption portion 220b. The base portion 220a may be closer to the surface of the semiconductor substrate having the structure 210 than the superadsorption portion 220b. The superadsorption portion 220b may be a material bonded on the base portion 220a.

The first portion 221a of the first preliminary unit layer 222 may be formed in an upper region of the structure 210, and the second portion 221b of the first preliminary unit layer 222 may be formed. It may be formed in the lower region of the structure 210. The first portion 221a of the first preliminary unit layer 222 may be formed on the upper side portion 210s1 of the structure 210, and the first portion of the first preliminary unit layer 222 may be formed. Two portions 221b may be formed on the lower side portion 210s2 of the structure 210.

The first precursor material 215 may be a material that is further stabilized by further bonding. For example, the first precursor material 215 may be a material capable of forming a cluster while making weak coordination bonds. The first precursor material 215 may be supplied into the process chamber 10 together with a carrier gas for transporting the first precursor material 215. The carrier gas may be an inert gas such as argon or the like.

The first precursor material 215 may be supplied into the process chamber 10 from the first process material supply device 20. The first process material supply device 20 may be a process material supply system of any one of the process material supply systems 20a, 20b, and 20c described with reference to FIGS. 2, 3, and 4. Thus, the precursor material 215 may be the same material as the precursor material 16 supplied from any of the process material supply systems 20a, 20b, 20c described in FIGS. 2, 3, and 4. .

25A and 25B in conjunction with FIGS. 8 and 24, the first preliminary formed by the first precursor material 215 and the first precursor material 215 supplied into the process chamber 10. The unit layer 222 will be described. The molecular structures shown in FIGS. 25A and 25B are illustrated as one example in order to facilitate understanding of the technical spirit of the present invention, and do not limit the technical spirit of the present invention.

8, 24, and 25A, the first precursor material 215 supplied into the process chamber 10 includes a central atom 215M and a first ligand 215L bound to the central atom 215M. ^a ) and the second ligand 215L ^b . The first precursor material 215 may be a material represented by M (L ^a ) _x (L ^b ) _y . The central atom 215M may be "M" at M (L ^a ) _x (L ^b ) _y , and the first ligand 215L ^a is selected from M (L ^a ) _x (L ^b ) _y 1 ligand "L ^a " and the second ligand 215L ^b may be the second ligand "L ^b " at M (L ^a ) _x (L ^b ) _y . The “x” and “y” may be numbers determined by the kind of the central atom 215M and the first and second ligands 215L ^a and 215L ^b . Any one of "x" and "y" may be zero or a positive number, and the other may be a positive number.

The first precursor material 215 may be, for example, a zirconium (Zr) precursor as shown in <Formula 1>. In the zirconium precursor, such as <Chemical Formula 1>, which may be used as the first precursor material 215, the central atom zirconium may be quadrupled.

<Chemical Structural Formula 1>

8, 24, and 25B, the first precursor material 215 may be adsorbed onto the surface of the semiconductor substrate having the structure 210 to form a first preliminary unit layer 222. The first preliminary unit layer 222 may include the first portion 221a and the second portion 221b. The first portion 221a of the first preliminary unit layer 222 may include the base portion 220a and the hyperadsorption portion 220b coupled to the base portion 220a.

The superadsorption portion 220b may be in weak coordination with the base portion 220a. An empty region 221v in which the first preliminary unit layer 222 is not formed may exist on the lower side portion 210s2 of the structure 210.

An over adsorption portion 220b may be formed on the upper side portion 210s1 of the structure 210, and the first precursor material 215 may be formed on the lower side portion 210s2 of the structure 210. The non-adsorbed empty region 221v may be formed. As shown in FIG. 22, the superadsorption portion 220b may be formed on the upper surface 210t of the structure 210 as well as the upper side portion 210s1 of the structure 210. Accordingly, the first preliminary unit layer 222 may be formed as a discontinuous layer by the empty region 221v, and the first preliminary unit layer 222 may be formed by the superadsorption portion 220b. Thus can be formed into a layer having a non-uniform thickness.

Meanwhile, a first precursor that is not adsorbed onto the surface of the semiconductor substrate 200 having the structure 210 in the process chamber 10 in which the semiconductor substrate 200 on which the first preliminary unit layer 222 is formed is located. 215a may remain.

1, 8, 22, 23, and 26, a film-controlled material 225 is supplied into the process chamber 10 in which a semiconductor substrate having the first preliminary unit layer 222 is located. Thus, the first preliminary unit layer 222 may be formed as the second preliminary unit layer 235. The second preliminary unit layer 235 may be formed of a uniform film as compared with the first preliminary unit layer 222. The film-control material 225 may start supplying the supply of the first precursor material 215 into the process chamber 10.

The superadsorption portion 220b may be combined with the film control material 225 to form a first compound 227. The first precursor material 215a remaining in the process chamber 10 may be combined with the film-control material 225 to form a second compound.

The film-controlled material 225 may be supplied into the process chamber 10 from the first process material supply device 20. The first process material supply device 20 may be a process material supply system of any one of the process material supply systems 20a, 20b, and 20c described with reference to FIGS. 2, 3, and 4. Thus, the film-controlled material 225 is the same as the film-controlled material 14 supplied from any of the process material supply systems 20a, 20b, 20c described in FIGS. 2, 3 and 4. It may be a substance. Since the type of the film-controlling materials 14 and 225 is described in the description of FIG. 2, detailed descriptions thereof will be omitted herein in order to avoid redundant description.

A method of forming the first preliminary unit layer 222 as the second preliminary unit layer 235 will be described with reference to FIGS. 25A, 25B, and 25C. 27A, 27B, and 27C are schematic views for easily understanding the technical spirit of the present invention. Note that the technical spirit of the present invention is not limited by the molecular structures shown in FIGS. 27A, 27B, and 27C. Do it. 27A, 27B, and 27C may be understood in connection with the contents described with reference to FIGS. 25A and 25B.

1, 8, 26, and 27a, the supply of the first precursor material 215 is stopped in the process chamber 10 in which the semiconductor substrate having the first preliminary unit layer 222 is located. The membrane-controlling material 225 may be supplied. After stopping the supply of the first precursor material 215 into the process chamber 10, the film-controlled material 225 in the process chamber 10 without a separate purge process to the process chamber 10. Can be supplied. The film-controlling material 225 may be a compound capable of breaking intermolecular bonds in the compound of the first precursor intermolecularly bonded (eg, the superadsorption portion 220b and the intermolecularly bound first precursor).

On the other hand, when the first precursor material 215 supplied into the process chamber 10 is a zirconium precursor such as <Formula 1>, in the zirconium precursor of <Formula 1>, in order to be stable Molecules of zirconium precursors can bind to each other. As such, the molecules of the zirconium precursor 215 may be bonded to each other, such that the superadsorption portion 220b may be formed in the first portion 221a of the first preliminary unit layer 222. In addition, since the molecules of the zirconium precursor 215 are bonded to each other to form a cluster, it may be prevented that the zirconium precursor 215 smoothly supplied into the lower region of the opening 210a.

As such, the zirconium precursors bonded to the molecules may be as shown in <Formula 2>. As shown in <Chemical Structural Formula 2>, the zirconium precursor may form a sixth coordinate in order to be in a stable molecular state.

<Chemical Structural Formula 2>

)일 수 있다. <Chemical Structural Formula 3> below is a chemical formula showing that the film-controlling material 225 is provided to the compound of <Chemical Structural Formula 2> which represents the intermolecularly bonded zirconium precursor. <Formula 3> is a chemical formula showing that the membrane-controlling material 225 is provided to the superadsorption portion 220b of the heterogeneous preliminary unit layer 222. Here, the film-controlling material 225 is a hydride (NMe ₂ ) of the ligand of the <Formula 1>

).

<Chemical Structural Formula 3>

1, 8, 26, and 27B, the membrane-controlling material 225 and the superadsorption portion 220b may react to form the first compound 227. In addition, the film-control material 225 may combine with the first precursor 215a or the intermolecularly coupled first precursor remaining in the empty space of the process chamber 10 to form a second compound 215b. have.

The first compound 227 and the second compound 215b may be compounds having the same kind of central atom as the first precursor material 215, and may be used as a precursor for forming a unit layer. Accordingly, the first and second compounds 227 and 215b may be defined as a second precursor material.

The superadsorption portion 220b may be separated from the base portion 220a while reacting with the film-control material 225 to form the first compound 227.

The first compound 227 may include a central atom 227M and one or more ligands 227L ^a , 227L ^b , and 225L bonded to the central atom 227M.

In addition, the second compound 215b may be a compound in which the first precursor 215a remaining in the empty space of the process chamber 10 and the film-control material 225 are combined. Alternatively, the second compound 215b is a compound bonded to the first precursor material while breaking the intermolecular bond of the first precursor material to which the film-controlling material 225 is intermolecularly coupled in the empty space of the process chamber 10. Can be. For example, the second compound 215b may include a central atom 215M and ligands 215L ^a , 215L ^b , and 225L bound to the central atom 215M. The film-control material 225 coupled with the first precursor 215a may be one ligand 225L of the ligands 215L ^a , 215L ^b , 225L of the second compound 215b. Meanwhile, the first precursor material 215 may include a center atom 215M and first and second ligands 215L ^a and 215L ^b bonded to the first center atom 215M.

The center atom 227M of the first compound 227, the center atom 215M of the second compound 215b, and the center atom 215M of the first precursor material 215 may be the same atom. Here, "the same atom" may mean the same atom in the atomic periodic table. For example, the center atom 227M of the first compound 227, the center atom 215M of the second compound 215b, and the center atom 215M of the first precursor material 215 may be Zr, Ti. , W, Ru or Al. Here, the technical idea of the present invention is not limited to "Zr, Ti, W, Ru or Al" as exemplified herein, and the center atom may be another metal atom.

Wherein said ligand of the first compound ^{(227) (227L a, 227L} b, 225L) any one of the ligand (225L) is the first of the ligands of the precursor material ^{(215) (215L a, 215L} b) and the other of The ligand may be a ligand, and the remaining ligands 227L ^a and 227L ^b may be formed of the same compound as the ligands 215L ^a and 215L ^b of the first precursor material 215.

The first compound 227 may be composed of a central atom 227M, a first ligand 227L ^a , a second ligand 227L ^b , and a third ligand 225L. The first ligand 227L ^a , the second ligand 227L ^b , and the third ligand 225L may be combined with the central atom 227M.

The central atom 227M of the first compound 227, the first ligand 227L ^a , and the second ligand 227L ^b may include the central atom 225M of the first precursor material 215, and the It may be the same as the first ligand 225L ^a and the second ligand 225L ^b . In addition, the third ligand 225L of the first compound 227 may be formed by combining the membrane-controlling material 225 with the central atom 227M.

The first compound 227 further includes the third ligand 225L additionally coordinated with respect to the first precursor material 215, thereby increasing the stability of the first precursor material 215. Can be.

)을 이용하여 상기 과흡착 부분(220b)을 상기 베이스 부분(220a)으로부터 분리함으로써 형성되는 상기 제1 및 제2 화합물들(227, 215b)의 일 예를 나타낸 화학구조식일 수 있다. 이러한 상기 제1 및 제2 화합물들(227, 215b)의 중심 원자 지르코늄은 6배위일 수 있다.<Chemical Structural Formula 4> is a chemical structural formula showing a state in which the film-controlling material 225 breaks bonds between the first precursor molecules 220a and 220b and forms coordination bonds. <Formula 4> is the membrane-controlling material (

It may be a chemical structural formula showing an example of the first and second compounds (227, 215b) formed by separating the superadsorption portion (220b) from the base portion (220a) by using. The central atom zirconium of the first and second compounds 227 and 215b may be six coordinating.

<Chemical Structural Formula 4>

The Chemical Formula 1 may represent the first precursor material 215, and the Chemical Formula 4 may represent the first and second compounds 227 and 215b.

)와 다른 리간드(

)를 포함할 수 있다. 상기 <화학구조식 4>의 상기 제1 및 제2 화합물(227, 215b)의 상기 리간드(

)는 상기 <화학구조식 1>의 상기 제1 전구체 물질(215)의 리간드(

)의 수소화물일 수 있다.The first precursor material 215 of Chemical Formula 1 and the first and second compounds 227 and 215b of Chemical Formula 4 may include the same central atom “Zr”. In addition, the first precursor material 215 of <Chemical Formula 1> and the first and second compounds 227 and 215b of <Chemical Formula 4> have the same kind of central atom "Zr" May have different ligands. For example, the first and second compounds 227 and 215b of Chemical Formula 4 may be ligands of the first precursor material 215 of Chemical Formula 1.

) And other ligands (

). The ligands of the first and second compounds 227 and 215b of <Formula 4>

) Is a ligand of the first precursor material 215 of <Formula 1>

Hydride).

The empty region 221v of the lower side portion 210s2 of the structure 210 with the first and second compounds 227 and 215b, that is, the second precursor, together with the remaining first precursor 215a. Can move up.

8, 26 and 27c, the first and second compounds 227 and 215b move onto the empty region 221v of the lower side portion 210s2 of the structure 210. Adsorbed on the empty region (221v) of the lower side portion 210s2. The portion 228a and the second compound 215b adsorbed on the surface of the structure 210 where the first compound 227 is exposed by the empty region 221v are exposed by the empty region 221v. An adsorbed portion 228b may be formed on the surface of the structure 210.

The portions 228a and 228b where the first and second compounds 227 and 215b are adsorbed on the surface of the structure 210 exposed by the empty region 221v are discontinuous in the first preliminary unit layer. 222 may be formed as the second preliminary unit layer 235.

In addition, the first adsorption portion 220b is separated and removed while the first compound 227 is formed, thereby forming the first preliminary unit layer 222 as the second preliminary unit layer 235 having a predetermined thickness. Can be. Accordingly, the first preliminary unit layer 222 may be formed to have a non-uniform thickness, but the second preliminary unit layer 235 may be formed to have a uniform thickness than the first preliminary unit layer 222. .

The first preliminary unit layer 222 may be formed by adsorbing the first precursor material 215 on a substrate having the structure 210, and the second preliminary unit layer 235 may be formed of the first precursor. The material 215 and the film-control material 225 may be formed of a material formed by further coordination coupling. Thus, the second preliminary unit layer 235 may further include the membrane-controlling material 225 as compared to the first preliminary unit layer 222. The second preliminary unit layer 235 may include a center atom 235M and a plurality of ligands 235L ^a , 235L ^b , and 225L bonded to the center atom 235M. Here, one of the plurality of ligands 235L ^a , 235L ^b , and 225L 225L may be formed by coupling the membrane-controlling material 225 to the central atom 235M.

1, 8, 22, 23, and 28, the process chamber 10 in which the semiconductor substrate 200 having the second preliminary unit layer 235 is located may be purged. (S315)

The second preliminary unit layer 235 may be formed as the unit layer 245 by supplying a second process material 240 into the purged process chamber 10. The reaction byproduct 247 may occur while forming the second preliminary unit layer 235 as the unit layer 245. The unit layer 245 may be formed by reacting the second process material 240 with a central atom of the second preliminary unit layer 235. Accordingly, the ligand and the film-controlling material of the precursor material 215 constituting the material other than the central atom of the second preliminary unit layer 235, for example, the second preliminary unit layer 235 ( 225 may be separated from the second preliminary unit layer 235 to constitute the reaction byproduct 247.

As described above with reference to FIG. 8, the second process material 240 may be supplied into the process chamber 10 from the second process material supply device 80. When the unit layer 245 is a metal-oxide, the second process material 240 includes ozone (O ₃ ), oxygen (O ₂ ), water vapor (H ₂ O), ozone plasma or oxygen plasma. It can be an oxidant. For example, the unit layer 245 may be a metal oxide such as titanium oxide, zirconium oxide, or ruthenium oxide. When the unit layer 245 is a metal-nitride such as titanium nitride or the like, the second process material 240 is a reaction gas such as ammonia (NH ₃ ), nitrogen dioxide (NO ₂ ) or nitrogen oxide (N ₂ O) or the like. Can be.

1, 8, 22, 23, and 29, the process chamber 10 in which the semiconductor substrate 200 on which the unit layer 245 is formed may be purged. The reaction byproduct 247 may be discharged to the outside of the process chamber 10 while purging the process chamber 10. The unit layer 245 may be repeatedly formed to form a deposition film 250 having a desired thickness.

30 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept. Another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIG. 30 along with FIGS. 8 and 9.

8, 9 and 30, the supply of the film-controlled material into the process chamber 10 before the first precursor is started, and the supply of the first precursor is supplied while the film-controlled material is supplied. After starting and stopping the supply of the film-controlled material, the supply of the first precursor may be stopped. Thus, the film-controlling material and the first precursor may be supplied together in the process chamber 10 for a period of time. Therefore, a preliminary unit layer may be formed on the semiconductor substrate by supplying a first process material including the film control material and the first precursor material to the process chamber 10. (S110) The process chamber 10 may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The process chamber 10 in which the semiconductor substrate on which the unit layer is formed is located may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer as one cycle may be repeatedly performed. Therefore, when the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed can be unloaded from the process chamber 10.

31 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept. Another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIG. 31 along with FIGS. 8 and 9.

8, 9 and 31, the supply of the first precursor material into the process chamber 10 before the film-controlled material is started, and the supply of the film-controlled material while the first precursor is supplied. After starting and stopping the supply of the first precursor, the supply of the film-controlled material may be stopped. Thus, the film-controlling material and the first precursor may be supplied together in the process chamber 10 for a period of time. Therefore, a preliminary unit layer may be formed on the semiconductor substrate by supplying a first process material including the film control material and the first precursor material to the process chamber 10. (S110) The process chamber 10 may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The process chamber 10 in which the semiconductor substrate on which the unit layer is formed is located may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer as one cycle may be repeatedly performed. Therefore, when the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed can be unloaded from the process chamber 10.

32 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept. Another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIG. 32 along with FIGS. 8 and 9.

8, 9, and 32, a first precursor and a film-controlled material may be simultaneously supplied into the process chamber 10. The first precursor and the film-controlled material may be simultaneously supplied to the process chamber 10 and may be stopped at the same time. Therefore, a preliminary unit layer may be formed on the semiconductor substrate by supplying a first process material including the film control material and the first precursor material to the process chamber 10. (S110) The process chamber 10 may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The process chamber 10 in which the semiconductor substrate on which the unit layer is formed is located may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer as one cycle may be repeatedly performed. Therefore, when the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed can be unloaded from the process chamber 10.

33 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept. Referring to FIG. 33 along with FIGS. 8 and 9, another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described.

8, 9 and 33, the supply of the film-controlled material into the process chamber 10 before the first precursor is started, and the supply of the first precursor is supplied while the film-controlled material is supplied. Start and stop the supply of the film-controlling material and the first precursor simultaneously. Therefore, a preliminary unit layer may be formed on the semiconductor substrate by supplying a first process material including the film control material and the first precursor material to the process chamber 10. (S110) The process chamber 10 may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The process chamber 10 in which the semiconductor substrate on which the unit layer is formed is located may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer as one cycle may be repeatedly performed. Therefore, when the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed can be unloaded from the process chamber 10.

34 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept. Another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIG. 34 along with FIGS. 8 and 9.

8, 9, and 34, the film-controlled material is supplied to the process chamber 10 before the first precursor, and the supply of the first precursor material is stopped while the supply of the film-controlled material is stopped. The film-controlling material may be supplied while the supply of the first precursor is stopped. The first precursor material may be supplied during the period in which the film control material is not supplied while supplying the film control material twice in the process chamber 10. Therefore, a preliminary unit layer may be formed on the semiconductor substrate by supplying a first process material including the film control material and the first precursor material to the process chamber 10. (S110) The process chamber 10 may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The process chamber 10 in which the semiconductor substrate on which the unit layer is formed is located may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer as one cycle may be repeatedly performed. Therefore, when the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed can be unloaded from the process chamber 10.

35 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept. Another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIG. 35 along with FIGS. 8 and 9.

8, 9, and 35, a first precursor material may be supplied in the middle of supplying the film-controlled material into the process chamber 10. The film-controlled material is supplied to the process chamber 10 before the precursor, and after a predetermined time, the first precursor material is supplied together with the film-controlled material, and even after the supply of the first precursor is stopped. Membrane-controlled materials can be supplied. Therefore, a preliminary unit layer may be formed on the semiconductor substrate by supplying a first process material including the film control material and the first precursor material to the process chamber 10. (S110) The process chamber 10 may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The process chamber 10 in which the semiconductor substrate on which the unit layer is formed is located may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer as one cycle may be repeatedly performed. Therefore, when the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed can be unloaded from the process chamber 10.

36 is a gas pulsing diagram illustrating still another example of a method of manufacturing a semiconductor device in accordance with an embodiment of the inventive concept. Another example of a method of manufacturing a semiconductor device according to an embodiment of the inventive concept will be described with reference to FIG. 36 along with FIGS. 8 and 9.

8, 9, and 36, the film-control material and the first precursor material may be simultaneously supplied into the process chamber 10, and the film-control material may be supplied for a longer time than the first precursor. Can be. Therefore, a preliminary unit layer may be formed on the semiconductor substrate by supplying a first process material including the film control material and the first precursor material to the process chamber 10. (S110) The process chamber 10 may be purged. The preliminary unit layer may be formed as a unit layer by supplying a second process material into the purged process chamber 10. The process chamber 10 in which the semiconductor substrate on which the unit layer is formed is located may be purged. When the desired deposition film thickness is not reached, the process of forming the unit layer as one cycle may be repeatedly performed. Therefore, when the desired deposition film thickness is reached, the semiconductor substrate on which the deposition film is formed can be unloaded from the process chamber 10.

37 is a cross-sectional view illustrating an example of a semiconductor device formed by a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 37, a structure 325 having a vertical side surface may be formed on the semiconductor substrate 300. Forming the structure 325 forms a mold insulating film 310, an opening 310a penetrating through the mold insulating film 310, and covers side and bottom surfaces of the opening 310a. It may include forming the first electrode 320. The first electrode 320 may be formed of a conductive material such as titanium nitride (TiN). The first electrode 320 may be formed using a deposition film formation method according to embodiments of the inventive concept.

The structure 325 may have an upper surface 325t, an upper side portion 325s1, and a lower side portion 325s2. The upper side portion 325s1 may mean a side portion positioned in an upper region of the structure 325, and the lower side portion 325s2 may mean a side portion positioned in a lower region of the structure 325. have.

The capacitor dielectric layer 330 may be formed on the semiconductor substrate having the structure 325. The capacitor dielectric film 330 may be a deposition film formed according to embodiments of the inventive concept. For example, the capacitor dielectric film 330 may be a deposition film formed according to any one of the embodiments of the inventive concept described with reference to FIGS. 1 to 34.

The second electrode 340 may be formed on the substrate having the capacitor dielectric layer 330. The second electrode 340 may be formed using a deposition film forming method according to embodiments of the inventive concept. The first electrode 320, the deposition film 330, and the second electrode 340 may constitute a capacitor.

38 is a cross-sectional view illustrating another example of a semiconductor device formed according to a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 38, a semiconductor substrate 400 may be prepared. The semiconductor substrate 400 may include an integrated circuit such as a MOS transistor.

An interlayer insulating film 405 may be formed on the semiconductor substrate 400. Conductive plugs 410 penetrating the interlayer insulating film 405 may be formed.

First electrodes 420 electrically connected to the conductive plugs 410 may be formed on the interlayer insulating layer 405.

Forming the first electrodes 420 forms a sacrificial mold film on the substrate having the conductive plugs 410, forms holes penetrating the sacrificial molding film, and forms a first on the substrate having the holes. The method may include forming an electrode film, planarizing the first electrode film to expose the sacrificial molding film, forming the first electrodes 420 remaining in the holes, and removing the sacrificial molding film. Here, the first electrode film may be formed using a deposition film forming method according to embodiments of the inventive concept. For example, the first electrode film may be formed by a deposition process using a hydrogen compound of a titanium precursor and a ligand of the titanium precursor.

The capacitor dielectric layer 430 may be formed on the substrate having the first electrodes 420. The capacitor dielectric film 430 may be formed using a deposition film forming method according to embodiments of the inventive concept. The second electrode 440 may be formed on the substrate having the capacitor dielectric layer 430. The second electrode 430 may be formed using a deposition film formation method according to embodiments of the inventive concept.

39 is a cross-sectional view illustrating still another example of a semiconductor device formed according to a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 39, an interlayer insulating film 505 may be formed on the semiconductor substrate 500. Conductive plugs 510 penetrating the interlayer insulating film 505 may be formed.

Cylindrical first electrodes 520 electrically connected to the conductive plugs 510 may be formed on the interlayer insulating layer 505. The first electrodes 520 may be formed using a deposition film formation method according to embodiments of the inventive concept. The capacitor dielectric layer 530 may be formed on the substrate having the first electrodes 520. The capacitor dielectric film 530 may be formed using a deposition film forming method according to embodiments of the inventive concept. The second electrode 540 may be formed on the substrate having the capacitor dielectric layer 530. The second electrode 530 may be formed using a deposition film forming method according to embodiments of the inventive concept.

40 is a cross-sectional view illustrating still another example of a semiconductor device formed according to a method of manufacturing a semiconductor device according to an embodiment of the inventive concept.

Referring to FIG. 40, interlayer insulating layers 610 stacked vertically on the semiconductor substrate 600 may be provided. Conductive patterns 670 may be interposed between the interlayer insulating layers 610.

A vertical structure 640 penetrating the conductive patterns 670 and the interlayer insulating layers 610 may be provided. The vertical structure 640 may include a core pattern 625, a pad pattern 630, and an outer pattern 620 that extends on a side surface of the pad pattern 630 and surrounds a side surface of the core pattern 625. Can be.

The core pattern 625 may be formed of an insulating material such as silicon oxide. When the core pattern 625 is formed of a dielectric by an ALD method, the core pattern 625 may be formed using a method of manufacturing a semiconductor device according to embodiments of the inventive concept.

The pad pattern 630 may be located on the core pattern 625 and at a level higher than the highest conductive pattern of the conductive patterns 670. The pad pattern 630 may be formed of a conductive material such as doped polysilicon.

The outer pattern 620 may include a semiconductor pattern that may serve as a channel of a transistor. For example, the outer pattern 620 may include a semiconductor material such as silicon. A portion of the outer pattern 620 that is close to the conductive patterns 670 may include a dielectric. The dielectric may include a material that can serve as a tunnel oxide film of a transistor, for example, silicon oxide. The dielectric may include a material capable of storing information of the flash memory device, for example, silicon nitride or a high dielectric material. The dielectric may be formed using a method of manufacturing a semiconductor device in accordance with embodiments of the inventive concept.

Meanwhile, the conductive patterns 670 may include a metal nitride film and / or a metal film. For example, each of the conductive patterns 670 may be formed of a metal film and a metal nitride film interposed between the metal film and the interlayer insulating films 610. In addition, the metal nitride film may extend between the metal film and the vertical structure 640. The conductive patterns 670 may be formed using a method of manufacturing a semiconductor device according to embodiments of the inventive concept.

A capping insulating layer 650 may be provided to cover the interlayer insulating layer 610 and the vertical structure 640.

According to embodiments of the inventive concept, a deposition film may be formed on a semiconductor substrate using a process including supplying a first process material including a film-control material and a precursor material into a process chamber. As described above, Sample 1-5 and Sample 6-10 were manufactured to describe the semiconductor device manufactured according to the method of manufacturing the semiconductor device according to the embodiments of the inventive concept.

Hereinafter, <Experimental Example 1> which produced Samples 1-5 and <Experimental Example 2> which produced Samples 6-10 will be described.

<Experimental Example 1>

Sample 2-5 having a deposition film formed by using both the film-controlling material and the precursor material and sample 1 in which a deposition film was formed using the precursor material without using the film-controlling material were prepared.

Samples 1-5 were formed by loading a semiconductor substrate into a process chamber, forming a deposition film while changing process conditions on the semiconductor substrate, and unloading the semiconductor substrate on which the deposition film was formed from the process chamber. The forming of the deposition film may include supplying a first process material into a process chamber in which a semiconductor substrate is located, purging the process chamber first, supplying ozone as an oxidant as a second process material into the process chamber, and Iteratively performing a process with a second cycle of purging the process chamber. Here, ozone as an oxidant was used as the second process material.

Samples 1-5 were formed using a first process material that commonly includes a zirconium precursor. Sample 1 was formed using a first process material that included the zirconium precursor without including the film-control material. Samples 2-5 were commonly formed using a first process material comprising the film-controlling material and the zirconium precursor.

Samples 1-5 were formed by vaporizing a liquid zirconium precursor in a liquid delivery system (LDS) to a temperature of 130 degrees and supplying it into the process chamber. In this case, in Sample 1-5, argon was used as a carrier gas for moving the zirconium precursor, and the flow rate of the zirconium precursor carrier gas was 160 sccm.

Samples 1-5 were commonly formed using zirconium precursors having the formula CpZr (N (CH ₃ ) ₂ ) ₃ , and samples 2-5 commonly used hydrogen compound DMA (dimethylamine) of the ligand of the zirconium precursor. . The DMA has the formula of HN (CH ₃ ) ₂ .

Samples 2-5 were commonly fed into the process chamber in gaseous form through a water filter with the dimethylamine (DMA) used as the membrane-controlling material. In Samples 2-4, the DMA used as the membrane control material was fed 1000 sccm in gaseous state through a water filter.

Samples 2-5 were prepared with varying methods of feeding the DMA (dimethylamine) into the process chamber.

Sample 1 is a sample in which zirconium oxide was formed using a zirconium precursor without using a film-controlling material. The zirconium oxide film having a thickness of 148 Å was formed by repeatedly performing 136 cycles of supplying the zirconium precursor into the process chamber, first purging the process chamber, supplying ozone as an oxidant, and purging the process chamber a second time. Sample 1 having was formed. The deposition rate of the zirconium oxide film in Sample 1 is 1.09 Å / cycle.

Sample 2 is a sample manufactured according to an embodiment of the inventive concept as described with reference to FIG. 32. As described in FIG. 32, the zirconium precursor and the film-controlled material are simultaneously supplied into the process chamber, followed by the first purge of the process chamber, followed by the supply of oxidant ozone into the process chamber, followed by the process chamber second. The sample 2, in which a zirconium oxide film having a thickness of 154 kPa was formed, was repeated 157 times to purge one cycle. The deposition rate of the zirconium oxide film in Sample 2 is 0.98 dl / cycle. In Sample 2, the zirconium precursor and the film-controlled material began to feed into the process chamber at the same time and at the same time stop feeding.

Sample 3 is a sample manufactured according to an embodiment of the inventive concept as described with reference to FIG. 22. As shown in FIG. 22, the zirconium precursor is supplied into the process chamber, the film-controlled material is supplied while the supply of the zirconium precursor is stopped, and then the purge of the process chamber is first performed, and then the oxidant ozone is supplied into the process chamber, Subsequently, the process of purging the process chamber secondly for one cycle was repeated 147 times to form Sample 3 in which a 152 Å thick zirconium oxide film was formed. The deposition rate of the zirconium oxide film in Sample 3 is 1.03 Å / cycle.

Sample 4 is a sample manufactured according to an embodiment of the inventive concept as described in FIG. 10. As described in FIG. 10, a film-controlled material is supplied into the process chamber, a zirconium precursor is supplied into the process chamber while the supply of the film-controlled material is stopped, and then the process chamber is first purged. The sample 4 in which a zirconium oxide film having a thickness of 146 kPa was formed was repeated 155 times by supplying an oxidizing agent ozone into the chamber and then purging the process chamber a second time. The deposition rate of the zirconium oxide film in the sample 4 is 0.64 Å / cycle.

Sample 5 is a sample manufactured according to an embodiment of the inventive concept as described with reference to FIG. 36. As described with reference to FIG. 36, after the film-controlled material and the zirconium precursor are simultaneously supplied into the process chamber, the supply of the zirconium precursor is stopped while the supply of the film-controlled material is continued, and the supply of the zirconium precursor is stopped. The process of stopping the supply of the membrane-controlled material, then purging the process chamber first, then supplying oxidant ozone into the process chamber, and then purging the process chamber a second time, is repeated 163 times. Thus, Sample 5 having a 147 Å thick zirconium oxide film was formed. The deposition rate of the zirconium oxide film in the sample 5 is 0.90 Å / cycle.

The result of measuring the thickness of the deposited film, that is, the zirconium oxide film in the sample 1-5 thus formed is shown in Table 1 below.

Cycle thickness Deposition rate One Sample 1 136 148 Å 1.09 Å / cycle 2 Sample 2 157 154 Å 0.98 Å / cycle 3 Sample 3 147 152 Å 1.03 Å / cycle 4 Sample 4 155 146 Å 0.94 Å / cycle 5 Sample 5 163 147 Å 0.90 Å / cycle

It can be seen that the sample 2-5 formed using the film control material has a smaller thickness of the unit layer deposited per cycle than the sample 1 which does not use the film control material. When performing the one cycle process, it can be seen that the unit layer thicknesses of Samples 2-5 are smaller than the unit layer thicknesses of Sample 1. In this experiment, the amount of zirconium precursor used per cycle is the same, and the film-controlling material is removed as the unit layer is formed. It can be seen that a unit layer close to a single atomic layer is formed when the deposition process is performed using a film-controlled material as in Sample 2-5, rather than the deposition process without using. In view of this, using the membrane-controlled material as in Sample 2-5 compared to Sample 1, the formation of the preliminary unit layer described in the embodiments of the present invention results in less superadsorption, which is an ideal step. It can be seen that a unit layer close to the atomic layer is formed.

<Experimental Example 2>

As described above, according to embodiments of the inventive concept, a deposition film is deposited on a semiconductor substrate using a process including supplying a first process material including a film-control material and a precursor material into a process chamber. Can be formed.

To fabricate Samples 6-10, the structure 325 as described in FIG. 37 is formed on a semiconductor substrate, a semiconductor substrate having the structure 325 is loaded into a process chamber, and the structure within the process chamber. A deposition film 330 was formed on the semiconductor substrate having 325, and the semiconductor substrate having the deposition film 330 was unloaded from the process chamber. As described above with reference to FIG. 37, the structure 325 may include a mold insulating layer 310 and a first electrode 320.

Supplying a first process material into a process chamber in which the semiconductor substrate having the structure 325 is located to form a preliminary unit layer, first purging the process chamber, and supplying a second process material into the process chamber The preliminary unit layer was formed as a unit layer, and the deposition film 330 of Sample 6-10 was formed by repeatedly performing a process in which a second purge of the process chamber was performed. Here, Sample 6-10 was formed while changing the process conditions for supplying the first process material.

Sample 6 is a sample in which the deposition film 330 is formed without using the film control material. Sample 7-10 uses both the film control material and the precursor material, but changes the method of supplying the film control material. While forming the deposition film 330 are samples. In this case, the precursor is a zirconium precursor having the formula CpZr (N (CH ₃ ) ₂ ) ₃ , and the film-controlling material is a hydrogen compound of the ligand of the zirconium precursor. The membrane-controlling substance is a ligand-hydrogen compound having the formula HN (CH ₃ ) ₂ .

In Samples 6-10, the liquid zirconium precursor was vaporized to a temperature of 130 degrees in a liquid delivery system (LDS) and fed into the process chamber. In Sample 6-10, the membrane-controlled material was fed 1000 sccm in gaseous state through a water filter. In Sample 6-10, argon was used as a carrier gas for moving the zirconium precursor, and the flow rate of the zirconium precursor carrier gas was 160 sccm.

Sample 6 is a sample in which the deposition film 330a is formed of zirconium oxide using a zirconium precursor without using a film control material. The zirconium precursor was supplied to the process chamber in the process chamber, the process chamber was first purged, ozone was supplied as an oxidant, and the process was performed in a cycle of repeating the process chamber for a second purge.

FIG. 41A illustrates a semiconductor device having a deposition film portion 330a_1 formed on the upper edge portion 325h of the structure 325 in Sample 6. FIG. The portion denoted by reference numeral 700a in FIG. 41A is a TEM photograph including the deposited film portion 330a_1 formed on the top edge portion 325h of the structure 325 in Sample 6, and denoted “Ha ′” in FIG. 41A. The displayed portion is an enlarged portion of the portion indicated by "Ha" of the TEM photograph 700a.

In sample 6, the thickness of the deposited film portion 330a_1 formed on the top edge portion 325h of the structure 325 is 136 Å.

FIG. 41B illustrates a semiconductor device having a portion 330a_2 of the deposited film formed on the upper side portion 325s_1 of the structure 325 in Sample 6. FIG. The portion indicated by reference numeral 700b in FIG. 41B is a TEM photograph that includes a portion 330a_2 of the deposited film formed on the upper side portion 325s_1 of the structure 325 in Sample 6, indicated by “Ua ′” in FIG. 41B. The portion is an enlarged portion of the portion labeled "Ua" in the TEM photograph 700b.

In Sample 6, the thickness of the deposited film portion 330a_2 formed on the upper side portion 325s_1 of the structure 325 is 129 kPa.

FIG. 41C illustrates a semiconductor device having a portion 330a_3 of a deposited film formed on the lower side portion 325s_2 of the structure 325 in Sample 6. FIG. The portion indicated by reference numeral 700c in FIG. 41C is a TEM photograph that includes the deposition film portion 330a_3 formed on the lower side portion 325s_2 of the structure 325 in Sample 6, and is labeled “La ′” in FIG. 41C. The portion is an enlarged portion of the portion labeled "La" of the TEM photograph 700c. In Sample 6, the thickness of the deposited film portion 330a_3 formed on the lower side portion 325s_2 of the structure 325 is 129 kPa.

Thus, in Sample 6, the deposited film portion 330a_1 formed on the upper surface edge portion 325h of the structure 325 was formed to have a first thickness of 136 Å, and the upper side portion of the structure 325 ( The deposition film portion 330a_2 formed on the 325s_1 was formed to have a second thickness of 129 μs, and the deposition film portion 330a_3 formed on the lower side portion 325s_2 of the structure 325 is the third thickness of 97 μs. It was formed to a thickness. In sample 6, the step coverage of the deposited film 330a is 71%.

In Sample 6-10, the step coverage of the deposited film was calculated from Equation 1 below.

Here, thickness 1 refers to the thickness of the deposition film portion formed on the upper edge portion 325h of the structure 325, and thickness 3 refers to the deposition formed on the lower side portion 325s_2 of the structure 325. The thickness of the membrane portion.

Sample 7 is a sample manufactured according to an embodiment of the inventive concept as described with reference to FIG. 32. The deposition film 330b of sample 7 simultaneously supplies a zirconium precursor and a film-controlled material into the process chamber, as described in FIG. 32, and then purges the process chamber first, then supplies oxidant ozone into the process chamber and Subsequently, it was formed by repeatedly performing a process in which a second cycle of purging the process chamber was performed. In sample 7, the zirconium precursor and the film-control material were fed for the same time.

FIG. 42A illustrates a semiconductor device having a deposition film portion 330b_1 formed on the upper edge portion 325h of the structure 325 in Sample 7. FIG. The portion indicated by reference numeral 710a in FIG. 42A is a TEM photograph including the deposited film portion 330b_1 formed on the top edge portion 325h of the structure 325 in Sample 7 and denoted as “Hb ′” in FIG. 42A. The displayed portion is an enlarged portion of the portion indicated by "Hb" of the TEM picture 710a. In sample 7, the thickness of the deposited film portion 330b_1 formed on the edge portion 325h of the top surface of the structure 325 is 138 kPa.

FIG. 42B illustrates a semiconductor device having a portion 330b_2 of the deposited film formed on the upper side portion 325s_1 of the structure 325 in Sample 7. FIG. The portion indicated by reference numeral 710b in FIG. 42B is a TEM photograph including the deposited film portion 330b_2 formed on the upper side portion 325s_1 of the structure 325 in Sample 7 and denoted by "Ua '" in FIG. 42B. The portion is an enlarged portion of the portion labeled "Ua" in the TEM photograph 710b.

In Sample 7, the thickness of the deposited film portion 330b_2 formed on the upper side portion 325s_1 of the structure 325 is 142 kPa.

FIG. 42C illustrates a semiconductor device having a portion 330b_3 of a deposition film formed on the lower side portion 325s_2 of the structure 325 in Sample 7. FIG. In FIG. 42C, the portion indicated by reference numeral 710c is a TEM photograph including the deposition film portion 330b_3 formed on the lower side portion 325s_2 of the structure 325 in Sample 7, and is indicated by “La ′” in FIG. 42C. The portion is an enlarged portion of the portion labeled "La" of the TEM photograph 710c. In sample 7, the thickness of the deposited film portion 330b_3 formed on the lower side portion 325s_2 of the structure 325 is 99 mm 3.

Accordingly, in sample 7, the deposition film portion 330b_1 formed on the upper surface edge portion 325h of the structure 325 was formed to have a first thickness of 138 kPa, and the upper side portion of the structure 325 ( The deposition film portion 330b_2 formed on the 325s_1 was formed to have a second thickness of 142 GPa, and the deposition film portion 330b_3 formed on the lower side portion 325s_2 of the structure 325 is the 99 s third. It was formed to a thickness. In sample 7, the step coverage of the deposited film 330b is 72%.

Sample 8 is a sample manufactured according to an embodiment of the inventive concept as described with reference to FIG. 22. The deposition film 330c of sample 8 supplies the zirconium precursor into the process chamber, stops the supply of the zirconium precursor and supplies the film-control material as described in FIG. 22, and then first purges the process chamber, It was formed by repeatedly carrying out a process in which an oxidizing agent ozone was supplied into the process chamber, and then a second cycle of purging the process chamber was performed.

FIG. 43A illustrates a semiconductor device having a deposition film portion 330c_1 formed on the upper edge portion 325h of the structure 325 in Sample 8. FIG. The portion indicated by reference numeral 720a in FIG. 43A is a TEM photograph including the deposition film portion 330c_1 formed on the upper edge portion 325h of the structure 325 in Sample 8, and denoted by “Hc ′” in FIG. 43A. The displayed portion is an enlarged portion of the portion indicated by "Hc" of the TEM picture 720a. In sample 8, the thickness of the deposited film portion 330c_1 formed on the edge portion 325h of the upper surface of the structure 325 is 134 kPa.

FIG. 43B illustrates a semiconductor device having a portion 330c_2 of the deposited film formed on the upper side portion 325s_1 of the structure 325 in Sample 8. FIG. The portion indicated by reference numeral 720b in FIG. 43B is a TEM photograph that includes a deposition film portion 330c_2 formed on the upper side portion 325s_1 of the structure 325 in Sample 8 and is designated as “Ua ′” in FIG. 43B. The portion is an enlarged portion of the portion labeled "Ua" in the TEM image 720b. In sample 8, the thickness of the deposited film portion 330c_2 formed on the upper side portion 325s_1 of the structure 325 is 123 kPa.

FIG. 43C illustrates a semiconductor device having a portion 330c_3 of the deposited film formed on the lower side portion 325s_2 of the structure 325 in Sample 8. FIG. The portion indicated by reference numeral 720c in FIG. 43C is a TEM photograph including the deposition film portion 330c_3 formed on the lower side portion 325s_2 of the structure 325 in Sample 8 and denoted by “La '” in FIG. 43C. The portion is an enlarged portion of the portion labeled "La" of the TEM photograph 720c. In sample 8, the thickness of the deposited film portion 330c_3 formed on the lower side portion 325s_2 of the structure 325 is 102 kPa.

Thus, in sample 8, the deposition film portion 330c_1 formed on the upper surface edge portion 325h of the structure 325 was formed to have a first thickness of 134 kPa, and the upper side portion of the structure 325 ( The deposition film portion 330c_2 formed on the 325s_1 was formed to have a second thickness of 123 mm 3, and the deposition film portion 330c_3 formed on the lower side portion 325s_2 of the structure 325 was formed to be 102 mm 3. It was formed to a thickness. In sample 8, the step coverage of the deposited film 330c is 76%.

Sample 9 is a sample prepared according to an embodiment of the inventive concept as described with reference to FIG. 10. The deposition film 330d of the sample 9 supplies a film-controlled material into the process chamber as described in FIG. 10, supplies a zirconium precursor into the process chamber while stopping the supply of the film-controlled material, and then the process chamber. After the first purge, the oxidizing agent ozone was supplied into the process chamber, and then the process of forming the second purge of the process chamber for the second cycle was repeatedly performed.

FIG. 44A illustrates a semiconductor device having a deposition film portion 330d_1 formed on the top edge portion 325h of the structure 325 in Sample 9. In FIG. 44A, the portion indicated by reference numeral 730a is a TEM photograph including the deposition film portion 330d_1 formed on the upper surface edge portion 325h of the structure 325 in Sample 9 and denoted as “Hc ′” in FIG. 44A. The displayed portion is an enlarged portion of the portion indicated by "Hc" of the TEM photograph 730a. In sample 9, the thickness of the deposited film portion 330d_1 formed on the edge portion 325h of the upper surface of the structure 325 is 122 kV.

FIG. 44B illustrates a semiconductor device having a portion 330d_2 of the deposited film formed on the upper side portion 325s_1 of the structure 325 in Sample 9. FIG. In FIG. 44B, the portion indicated by reference numeral 730b is a TEM photograph including the deposition film portion 330d_2 formed on the upper side portion 325s_1 of the structure 325 in Sample 9 and denoted by “Ua ′” in FIG. 44B. The portion is an enlarged portion of the portion labeled "Ua" in the TEM photograph 730b. In sample 9, the thickness of the deposited film portion 330d_2 formed on the upper side portion 325s_1 of the structure 325 is 117 mm 3.

FIG. 44C illustrates a semiconductor device having a portion 330d_3 of a deposition film formed on the lower side portion 325s_2 of the structure 325 in Sample 9. FIG. In FIG. 44C, the portion indicated by reference numeral 730c is a TEM photograph including the deposition film portion 330d_3 formed on the lower side portion 325s_2 of the structure 325 in Sample 9, and is indicated by “La ′” in FIG. 44C. The portion is an enlarged portion of the portion labeled "La" of the TEM photograph 730c. In sample 9, the thickness of the deposited film portion 330d_3 formed on the lower side portion 325s_2 of the structure 325 is 102 kPa.

Thus, in Sample 9, the deposition film portion 330d_1 formed on the upper surface edge portion 325h of the structure 325 was formed to have a first thickness of 122 Å, and the upper side portion of the structure 325 ( The deposition film portion 330d_2 formed on the 325s_1 was formed to have a second thickness of 117 mm 3, and the deposition film portion 330d_3 formed on the lower side portion 325s_2 of the structure 325 was 102 mm 3. It was formed to a thickness. In sample 9, the step coverage of the deposited film 330d is 84%.

The sample 10 is a sample manufactured according to an embodiment of the inventive concept as described with reference to FIG. 36. The deposition film 330e of the sample 10 simultaneously supplies the film-control material and the zirconium precursor into the process chamber as described with reference to FIG. 36, stops the supply of the zirconium precursor while continuing to supply the film-control material, Stopping supply of the zirconium precursor and then stopping supply of the film-controlled material, and then purging the process chamber first, then supplying oxidant ozone into the process chamber, and subsequently purging the process chamber a second time. It was formed by repeating the step to 1 cycle.

45A illustrates a semiconductor device having a deposition film portion 330e_1 formed on the top edge portion 325h of the structure 325 in Sample 10. The portion indicated by reference numeral 740a in FIG. 45A is a TEM photograph including the deposited film portion 330e_1 formed on the top edge portion 325h of the structure 325 in Sample 10, and denoted as "Hc" in FIG. 45A. The displayed portion is an enlarged portion of the portion indicated by "Hc" of the TEM photograph 740a. In Sample 10, the thickness of the deposited film portion 330e_1 formed on the edge portion 325h of the top surface of the structure 325 is 135 kPa.

45B illustrates a semiconductor device having a portion 330e_2 of a deposited film formed on the upper side portion 325s_1 of the structure 325 in sample 10. In FIG. 45B, the portion indicated by reference numeral 740b is a TEM photograph including the deposition film portion 330e_2 formed on the upper side portion 325s_1 of the structure 325 in Sample 10 and denoted by “Ua ′” in FIG. 45B. The portion is an enlarged portion of the portion labeled "Ua" in the TEM photograph 740b. In sample 10, the thickness of the deposited film portion 330e_2 formed on the upper side portion 325s_1 of the structure 325 is 129 μs.

FIG. 45C illustrates a semiconductor device having a portion 330e_3 of a deposited film formed on the lower side portion 325s_2 of the structure 325 in sample 10. In FIG. 45C, the portion indicated by reference numeral 740c is a TEM photograph including the deposition film portion 330e_3 formed on the lower side portion 325s_2 of the structure 325 in Sample 10 and denoted by “La ′” in FIG. 45C. The portion is an enlarged portion of the portion labeled "La" of the TEM photograph 740c. In sample 10, the thickness of the deposited film portion 330e_3 formed on the lower side portion 325s_2 of the structure 325 is 104 kPa.

In sample 10, the first thickness of the deposited film portion 330e_1 on the top edge portion 325h of the structure 325 is 135 microns, and on the upper side portion 325s_1 of the structure 325. The second thickness of the deposited film portion 330e_2 is 129 kPa, and the third thickness of the deposited film portion 330e_3 on the lower side portion 325s_2 of the structure 325 is 104 kPa. In the sample 10, the step coverage of the deposition film 330e is 77%.

Table 2 below shows the results of TEM analysis on Samples 6-10. In Table 2, the first thickness HT is a thickness of the deposition film 330 of Sample 6-10 formed on the upper edge portion 325h of the structure 325, and the second thickness UT is The thickness of the deposition film 330 of Sample 6-10 formed on the upper side portion 325s_1 of the structure 325, and the third thickness LT is on the lower side portion 325s_2 of the structure 325. Thickness of the deposited film 330 of Samples 6-10 formed.

First thickness (HT) 2nd thickness (UT) Third thickness (LT) Step Coverage (LT / HT) One Sample 6 136Å 129 yen 97 yen 71% 2 Sample 7 138 yen 142Å 99Å 72% 3 Sample 8 134 yen 123 yen 102Å 76% 4 Sample 9 122 yen 117 yen 102Å 84% 5 Sample 10 135Å 129 yen 104Å 77%

From Samples 6-10, the deposition films in Sample 7-10, which were deposited using the film-controlled material rather than the deposition film 330a of Sample 6, which did not use the film-controlled material, It can be seen that the step coverage of 330b, 330c, 330d, and 330e is excellent.

The second thickness UT of the deposition film formed on the upper side portion 325s_1 of the structure 325 and the third thickness of the deposition film formed on the lower side portion 325s_2 of the structure 325. The ratio of (LT) was calculated using Equation 2 below.

In Sample 6, when the ratio of the third thickness LT and the second thickness UT is calculated using Equation 2, the ratio is 75%. In sample 8, when the ratio of the third thickness LT and the second thickness UT is calculated using Equation 2, the ratio is 83%. When the ratio of the third thickness LT and the second thickness UT is calculated, the ratio is 87%. In Sample 10, the third thickness LT and the second thickness UT are calculated using Equation 2. The percentage is 81%. Accordingly, the deposition films 330c, 330d, and 330e of the sample 8-10 manufactured according to the embodiments of the inventive concept have better step coverage characteristics than the sample 6, and the overall deposition of the deposition film as compared to the sample 6. It can be seen that the uniformity is excellent.

FIG. 46 is a view schematically illustrating a memory card having a semiconductor device formed by a method of manufacturing a semiconductor device according to embodiments of the inventive concept.

Referring to FIG. 46, the memory card 800 may include a card substrate 810, one or more semiconductor devices 830 disposed on the card substrate 810, and one edge of the card substrate 810. The contact terminals 820 may be formed in parallel with each other and electrically connected to the semiconductor devices 830, respectively. Here, the semiconductor device 830 may include a deposition film formed according to embodiments of the inventive concept. The semiconductor device 830 may be a component in the form of a memory chip or a semiconductor package.

The memory card 800 may be a memory card for use in an electronic device, for example, a digital camera, a tablet PC, a computer, a portable storage device, or the like.

The card substrate 810 may be a printed circuit board (PCB). Both sides of the card substrate 810 may be used. For example, semiconductor devices 830 may be disposed on both front and rear surfaces of the card substrate 810. The semiconductor device 830 may be electrically and mechanically connected to the card substrate 810 on the front and / or rear surface of the card substrate 810.

The contact terminals 820 may be formed of metal and may have oxidation resistance. The contact terminals 820 may be variously set according to the type and standard of the memory card 800. Therefore, the number of contact terminals 820 shown does not have a special meaning.

47 is a block diagram illustrating an electronic system having a semiconductor device formed by a method of manufacturing a semiconductor device according to example embodiments of the inventive concepts.

Referring to FIG. 47, an electronic device 900 may be provided. The electronic device 900 may include a processor 910, a memory 920, and an input / output device (I / O) 930. The processor 910, the memory 920, and the input / output device 930 may be connected through a bus 946.

The memory 920 may receive a control signal such as RAS *, WE *, CAS *, etc. from the processor 910. The memory 920 may store codes and data for the operation of the processor 910. The memory 920 may be used to store data accessed via the bus 946.

The memory 920 may include a deposition film formed according to embodiments of the inventive concept. The processor 910 may include a deposition film formed according to embodiments of the inventive concept.

The electronic device 900 may configure various electronic control devices that require the memory 920. For example, the electronic device 900 may be a computer system, a wireless communication device such as a PDA, a laptop computer, a portable computer, a web tablet, a cordless phone, a mobile phone, a digital music player. player, MP3 player, navigation, solid state disk (SSD), household appliance, or any device capable of transmitting and receiving information in a wireless environment.

A more specific implementation and modified example of the electronic device 900 will be described with reference to FIG. 46.

48 is a block diagram illustrating a data storage device having a semiconductor device formed by a method of manufacturing a semiconductor device according to example embodiments of the inventive concepts.

Referring to FIG. 48, the electronic device may be a data storage device such as a solid state disk (SSD) 1011. The solid state disk (SSD) 1011 may include an interface 1013, a controller 1015, a non-volatile memory 1018, and a buffer memory 1019.

The solid state disk 1011 may be a device that stores information using a semiconductor device. The solid state disk 1011 is faster than a hard disk drive (HDD), has less mechanical delay, failure rate, heat generation, and noise, and can be miniaturized / lightened. The solid state disk 1011 may be used in a notebook PC, netbook, desktop PC, MP3 player, or portable storage device.

The controller 1015 may be formed adjacent to the interface 1013 and electrically connected to the interface 1013. The controller 1015 may be a microprocessor including a memory controller and a buffer controller. The controller 1015 may include a deposition film formed by a method of manufacturing a semiconductor device according to embodiments of the inventive concept.

The non-volatile memory 1018 may be formed adjacent to the controller 1015 and electrically connected to the controller 1015 via a connection terminal T. The data storage capacity of the solid state disk 1011 may correspond to the non-volatile memory 1018. The buffer memory 1019 may be formed adjacent to the controller 1015 and electrically connected to the controller 1015.

The interface 1013 may be connected to a host 1002 and may transmit and receive electrical signals such as data. For example, the interface 1013 may be a device using a standard such as SATA, IDE, SCSI, and / or a combination thereof. The non-volatile memory 1018 may be connected to the interface 1013 via the controller 1015.

The non-volatile memory 1018 may serve to store data received through the interface 1013. The non-volatile memory 1018 may include a deposition film formed according to embodiments of the inventive concept. Even if power is supplied to the solid state disk 1011, data stored in the non-volatile memory 1018 is preserved.

The buffer memory 1019 may include a volatile memory. The volatile memory may be a dynamic random access memory (DRAM), and / or a static random access memory (SRAM). The buffer memory 1019 shows a relatively faster operating speed than the non-volatile memory 1018. The buffer memory 1019 may include a deposition film formed according to embodiments of the inventive concept.

The data processing speed of the interface 1013 may be relatively faster than the operating speed of the non-volatile memory 1018. Here, the buffer memory 1019 may serve to temporarily store data. The data received through the interface 1013 is temporarily stored in the buffer memory 1019 via the controller 1015 and then adjusted to the data write speed of the non-volatile memory 1018. Permanent storage in volatile memory 1018. In addition, frequently used data among the data stored in the non-volatile memory 1018 may be read in advance and temporarily stored in the buffer memory 1019. That is, the buffer memory 1019 may play a role of increasing the effective operating speed of the solid state disk 1011 and reducing an error occurrence rate.

49 is a diagram illustrating an electronic system according to an embodiment of the inventive concept.

Referring to FIG. 49, an electronic device 1100 may include a storage device 1110, a control device 1120, and an input / output device 1130. The input / output device 1130 may include an input device 1133, a display device 1136, and a wireless communication device 1139.

The storage device 1110 may be one or more different types of storage devices, such as hard disk drive storage, non-volatile memory (eg, flash memory or other EEPROM), volatile memory (eg, battery based SDRAM or DRAM), or the like. It may include. The storage device 1110 may include a deposition film formed by embodiments of the inventive concept.

The control device 1120 may be used to control the operation of the electronic device 1100. For example, the control device 1120 may include a microprocessor. The control device 1120 may include a deposition film formed by embodiments of the inventive concept.

The input / output device 1130 may include an input device 1133, a display device 1136, and a wireless communication device 1139.

The input / output device 1130 may be used to supply data to the electronic device 1100 and to provide data from the electronic device 1100 to external devices. For example, it may include a display screen, a button and a port, a touch screen, a joystick, a click wheel, a scrolling wheel, a touch pad, a keypad, a keyboard, a microphone, a camera, and the like.

The wireless communication device 1139 is a communication circuit, such as a radio-frequency (RF) transceiver circuit, formed of one or more integrated circuits, power amplifier circuits, passive RF components, one or more antennas, and other circuitry for processing RF radio signals. It may include. Wireless signals may also be transmitted using light (eg, using infrared communication). The wireless communication device 1139 may include a deposition film formed by embodiments of the inventive concept.

50 is a diagram schematically illustrating a mobile wireless phone 1200 including a semiconductor device manufactured by a method of manufacturing a semiconductor device according to embodiments of the inventive concept. The mobile wireless phone 1200 may be understood as a tablet PC. In addition to the tablet PC, the semiconductor device according to an embodiment of the present invention can also be used as a portable computer such as a notebook, a mpeg-1 audio layer 3 (MP3) player, an MP4 player, a navigation device, a solid state disk Table computers, automobiles and household appliances.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You can understand that you can. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (20)

Loading the semiconductor substrate into the process chamber,
Forming a deposition film on the semiconductor substrate in the process chamber, wherein forming the deposition film includes repeatedly forming a unit layer on the semiconductor substrate,
Unloading the semiconductor substrate on which the deposition film is formed from the process chamber,
Forming the unit layer is
Supplying a process material comprising a precursor material and a film-control material into the process chamber to form a preliminary unit layer on the semiconductor substrate, wherein the precursor material comprises a central atom and a ligand bonded to the central atom, The membrane-controlling material is a hydrogen compound of the ligand of the precursor material,
First purging the process chamber in which the semiconductor substrate having the preliminary unit layer is located,
Forming the preliminary unit layer in the first purged process chamber as a unit layer,
And second purging the process chamber in which the semiconductor substrate having the unit layer is located. The method of claim 1,
The precursor material is adsorbed on the semiconductor substrate to form a precursor adsorption layer. 3. The method of claim 2,
And the film-controlling material is coordinated with a central atom of the precursor adsorption layer to form the precursor adsorption layer as a chemically more stable material than the precursor adsorption layer. The method of claim 1,
Forming the preliminary unit layer
Supplying the precursor material into the process chamber to form a precursor adsorption layer on the semiconductor substrate, wherein the precursor adsorption layer comprises a base portion and a supersorption portion coupled to the base portion,
Supplying said film-controlled material into said process chamber to separate said hyperadsorbed portion from said base portion. 5. The method of claim 4,
And the film-controlling material bonds with the central atom of the superadsorption portion while breaking the bond between the superadsorption portion and the base portion. The method of claim 1,
The preliminary unit layer includes both the precursor material and the film control material. The method according to claim 6,
The ligand of the precursor material and the membrane-controlling material constituting the preliminary unit layer are separated from the preliminary unit layer while forming the preliminary unit layer as the unit layer, and are formed as reaction byproducts,
The reaction by-products are removed while the second purge the process chamber. The method of claim 1,
The ligand includes a first ligand and a second ligand bonded to the central atom, wherein the first ligand and the second ligand have different formulas,
And the film-controlling material is a hydrogen compound of the first ligand. Loading the semiconductor substrate into the process chamber,
Forming a deposition film on the semiconductor substrate in the process chamber, wherein forming the deposition film includes repeatedly forming a unit layer on the semiconductor substrate,
Unloading the semiconductor substrate with the deposition film from the process chamber,
Forming the unit layer is
Supplying a first film-control material into the process chamber to form a surface-control layer on the semiconductor substrate,
Supplying a precursor material into the process chamber to form a precursor adsorption layer adsorbed to the surface-control layer to form a preliminary unit layer comprising the surface-control layer and the precursor adsorption layer, wherein the precursor material comprises a central atom and Is a compound containing a ligand bonded to the central atom,
First purging the process chamber in which the semiconductor substrate having the preliminary unit layer is located,
Forming the preliminary unit layer as a unit layer while separating the ligands in the surface-control layer and the precursor adsorption layer to form reaction byproducts,
Removing the reaction by-products while purging the process chamber in which the semiconductor substrate having the unit layer is located. The method of claim 9,
And supplying the first precursor in a state where the first film-control material is present in the process chamber. The method of claim 9,
Supplying a second film-controlled material into the process chamber prior to stopping the supply of the precursor material into the process chamber and prior to the first purging of the process chamber,
And the second film-control material is a material that coordinates with the central atom of the precursor material. Forming a semiconductor substrate having a structure, the structure having vertical side portions,
Loading a semiconductor substrate having the structure into a process chamber,
Forming a deposition film on the semiconductor substrate having the structure in the process chamber, wherein forming the deposition film includes repeatedly forming a unit layer on the semiconductor substrate having the structure,
Unloading the semiconductor substrate with the deposition film from the process chamber,
Forming the unit layer is
Supplying a first precursor material to the process chamber to form a first preliminary unit layer to which the first precursor material is adsorbed on a semiconductor substrate having the structure, wherein the first preliminary unit layer comprises a base portion and the base portion; A physically coupled superabsorbent portion,
Supplying a membrane-controlled material into the process chamber to form the first preliminary unit layer as a second preliminary unit layer, wherein a portion of the membrane-controlled material reacts with the first preliminary unit layer to form the superadsorbed portion. Forming a second precursor material while separating from the base portion,
Purging the process chamber in which the semiconductor substrate having the second preliminary unit layer is located,
Forming the second preliminary unit layer as a unit layer,
And purging a process chamber in which the semiconductor substrate having the unit layer is located. 13. The method of claim 12,
The first precursor material is a first compound comprising a central atom and a ligand bound to the central atom,
Wherein a portion of the film-controlled material is combined with a central atom of the superadsorbed portion to form the second precursor material while separating the superadsorbed portion from the base portion. The method of claim 13,
A portion of the film-controlling material is bonded to a central atom of the base portion to increase the coordination number of the central atoms of the base portion. The method of claim 13,
The semiconductor substrate having the first preliminary unit layer includes a blank region in which the precursor material is not adsorbed. The method of claim 15,
Forming the second preliminary unit layer includes adsorbing the second precursor material onto the semiconductor substrate in the empty region. The method of claim 15,
And the over-adsorption portion is formed in an upper region of the structure, and the empty region is formed in a lower region of the structure located at a lower level than the over-adsorption portion. Loading the semiconductor substrate into the process chamber,
Forming a deposition film on the semiconductor substrate in the process chamber, the deposition film comprising repeatedly forming a unit layer on the semiconductor substrate,
Unloading the semiconductor substrate on which the deposition film is formed from the process chamber,
Forming the unit layer is
Supplying a first process material comprising a film-controlling material and a precursor material into the process chamber to form a preliminary unit layer, wherein the precursor material comprises a first atom comprising a central atom and a ligand bound to the central atom; Compound, wherein the preliminary unit layer includes a second compound formed by combining the precursor material and the film control material,
First purging the process chamber in which the semiconductor substrate having the preliminary unit layer is located,
Forming the preliminary unit layer in the first purged process chamber as a unit layer, wherein the ligand and the membrane-controlled material in the second compound are separated from the preliminary unit layer while forming the preliminary unit layer as the unit layer. To form reaction byproducts,
And removing the reaction by-products while purging the process chamber in which the semiconductor substrate having the unit layer is located. The method of claim 18,
While forming the preliminary unit layer,
Precursor molecules of the precursor material combine with each other in the process chamber to form a precursor cluster,
And the film-controlling material bonds with molecules of the precursor cluster while forming bonds between molecules of the precursor cluster to form the second compound. The method of claim 18,
Forming the preliminary unit layer includes proceeding in a process atmosphere in which the first compound, the film-controlling material, and the second compound coexist.

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