Method for forming oxide film, method for manufacturing semiconductor device, method for forming dielectric film, and semiconductor device

Abstract

Disclosed are a method of forming an oxide film including at least two non-oxygen elements, a method of manufacturing a semiconductor device, a method of forming a dielectric film, and a semiconductor device. The method of forming an oxide film including at least two non-oxygen elements includes providing a first source material on a substrate, the first source material including a first central element; providing an electron donor compound to combine with the first source material; providing a second source material on the substrate after providing the electron donor compound, the second source material including a second central element; and providing an oxidizing agent on the substrate.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2019-0091159, filed July 26, 2019, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. TECHNICAL FIELD

[0003] The present inventive concept relates to a method of forming an oxide film including at least two non-oxygen elements, a method of manufacturing a semiconductor device, a method of forming a dielectric film (electrical dielectric film), and a semiconductor device, and more particularly, to a method of manufacturing a high-aspect-ratio material film including at least two non-oxygen elements to have high uniformity in composition and size, and a semiconductor device manufactured by using the method. BACKGROUND

[0004] As the complexity of semiconductor devices is increased and the performance of semiconductor devices is required to be enhanced, an oxide material film having at least two metals or semimetals, which has good or high uniformity in composition and size, can be advantageous. In particular, as the aspect ratio of a feature on which a material film is to be deposited is greatly increased, it can become more difficult to satisfy the above need. SUMMARY

[0005] The present inventive concept provides a method of forming an oxide film by which a high-aspect-ratio material film including at least two non-oxygen elements can be formed to have high uniformity in composition and size.

[0006] The present inventive concept also provides a method of manufacturing a semiconductor device by which a high-aspect-ratio material film including at least two non-oxygen elements can be formed to have high uniformity in composition and size.

[0007] In addition, the present inventive concept provides a method of forming a dielectric film by which a high-aspect-ratio material film including at least two non-oxygen elements can be formed to have high uniformity in composition and size.

[0008] Furthermore, the present inventive concept provides a semiconductor device including a high-aspect-ratio material film including at least two non-oxygen elements, and the high-aspect-ratio material film can have high uniformity in composition and size.

[0009] According to one aspect of the inventive concept, there is provided a method of forming an oxide film including at least two non-oxygen elements. The method includes providing a first source material including a first central element on a substrate, providing an electron donor compound to bind with the first source material, providing a second source material including a second central element on the substrate after providing the electron donor compound, and providing an oxidizing agent on the substrate. The at least two non-oxygen elements included in the oxide film can include the first central element in the first source material and the second central element in the second source material. The first central element in the first source material and the second central element in the second source material can be different from each other.

[0010] According to another aspect of the inventive concept, there is provided a method of manufacturing a semiconductor device. The method includes forming a lower electrode electrically connected with an active region of a semiconductor substrate, forming a dielectric film on an entire exposed surface of the lower electrode, and forming an upper electrode on the dielectric film. The forming of the dielectric film includes providing a first source material on the exposed surface of the lower electrode, providing an electron donor compound capable of forming a van der Waals bond with the first source material, providing a second source material on the lower electrode after providing the electron donor compound, and providing an oxidizing agent on the lower electrode.

[0011] According to another aspect of the inventive concept, there is provided a method of forming a dielectric film. The method includes providing a substrate into a reaction chamber, providing a first electron donor compound on the substrate, and repeating a deposition cycle until an oxide film is formed on the substrate to a set thickness. The deposition cycle includes providing a first source material including a first central element on the substrate, providing a second electron donor compound to bind with the first source material, providing a second source material including a second central element on the substrate after providing the second electron donor compound, and providing an oxidizing agent on the substrate. The first and second electron donor compounds can be the same as or different from each other, and can each independently be as defined below for an electron donor compound.

[0012] According to another aspect of the inventive concept, there is provided a semiconductor device including at least two lower electrodes formed on a substrate, a dielectric film formed on a surface of the at least two lower electrodes, the dielectric film including at least two metal elements or semi-metal elements, and an upper electrode formed on the dielectric film and electrically insulated from the at least two lower electrodes. An aspect ratio of the lower electrode ranges from about 30 to about 200, and a ratio of a minimum thickness of the dielectric film to a maximum thickness of the dielectric film is 0.93 or more. The semiconductor device can be obtained by the above-described method of manufacturing a semiconductor device. BRIEF DESCRIPTION OF DRAWINGS

[0013] Example embodiments of the inventive concept will be more clearly understood from the following detailed description considered in connection with the accompanying drawings, in which:

[0014] Figure 1 a flowchart of a method of forming an oxide film according to an example embodiment;

[0015] Figure 2 a detailed flowchart of operations of forming an oxide film on a substrate according to an example embodiment;

[0016] Figures 3A-3D a schematic conceptual diagram to explain a mechanism of uniformly forming an oxide film on a substrate;

[0017] Figure 4 a schematic diagram of a semiconductor apparatus configured to perform a method of forming a material film according to an example embodiment;

[0018] Figures 5A-5F a timing chart to explain a configuration of a supply cycle of a first source material, a second source material, an electron-donating compound, and an oxidizing agent according to an example embodiment;

[0019] Figures 6A-6H a side view cross-sectional diagram of a process sequence of a method of manufacturing a semiconductor device according to an example embodiment;

[0020] Figure 7 a flowchart of a method of forming an oxide film according to an example embodiment;

[0021] Figures 8A-8E a schematic conceptual diagram of respective operations of a process of forming an oxide film on a lower electrode of Figure 6G

[0022] a diagram to schematically explain a concentration of a first central element and a concentration of a second central element in a capacitor dielectric film with respect to a z-axis position of Figure 9A Figure 8E Figure 8E a diagram to schematically explain a concentration of a first central element and a concentration of a second central element in a capacitor dielectric film with respect to a z-axis position of

[0023] Figure 9B a diagram to schematically explain a concentration of a first central element and a concentration of a second central element in a capacitor dielectric film with respect to a z-axis position of

[0024] Figures 10A-10C a diagram to explain a method of manufacturing a semiconductor device according to an example embodiment, in which Figure 10A a top view of a formed semiconductor device, Figure 10B a perspective view of a semiconductor device of Figure 10A Figure 10C a perspective view of a semiconductor device of Figure 10C a perspective view of a semiconductor device ofFigure 10A A cross-sectional view of the cross-sectional structure taken along lines XX' and YY'; and

[0025] Figure 11 is a cross-sectional view of another example of a semiconductor device formed by using a method of manufacturing a semiconductor device according to example embodiments. DETAILED DESCRIPTION

[0026] When the term "about" or "substantially" is used in this specification with respect to a numerical value, it is intended that the relevant numerical value includes a tolerance of ±10% around the stated numerical value. When a range is stated, the range includes all values ​​therebetween, for example in increments of 0.1%.

[0027] Hereinafter, example embodiments will be described in detail with reference to the accompanying drawings. The same reference numerals are used to denote the same elements in the drawings, and repeated description thereof will be omitted.

[0028] Figure 1 is a flowchart of a method of forming an oxide film according to example embodiments.

[0029] Reference Figure 1 , a substrate may be loaded into a reaction chamber (S1). The substrate may include a semiconductor substrate comprising a semiconductor element (e.g., silicon (Si) or germanium (Ge)) or a compound semiconductor (e.g., silicon carbide (SiC), gallium arsenide (GaAs), indium arsenide (InAs), or indium phosphide (InP)). In some example embodiments, the substrate may include a semiconductor substrate, at least one insulating film formed on the semiconductor substrate, and / or a structure (structure) comprising at least one conductive region. The conductive region may include, for example, a doped well, a doped structure, and / or a conductive layer containing a metal. In addition, the substrate may have one of a variety of device isolation structures, such as a shallow trench isolation (STI) structure.

[0030] An oxide film may be formed on the substrate loaded into the reaction chamber (S2). The oxide film may include a metal oxide and / or a semi-metal oxide.

[0031] In some example embodiments, the oxide film can contain at least two metals and / or semimetals, for example, the oxide film can contain a material represented by MxM'yOz. Here, M and M' each can independently represent a metal or a semimetal and can include at least one selected from the group consisting of beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), rubidium (Rb), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), cesium (Cs), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), polonium (Po), francium (Fr), radium (Ra), actinium (Ac), thorium (Th), protactinium (Pa), and uranium (U). x, y, and z each represent the relative content of M, M', and oxygen, respectively. x, y, and z each are a real number greater than zero (0) and are not particularly limited.

[0032] For example, the oxide film can include a zirconium-silicon oxide film, a hafnium-silicon oxide film, an aluminum-silicon oxide film, a lanthanum-silicon oxide film, a tantalum-silicon oxide film, or a combination thereof.

[0033] The oxide film manufactured by the method of forming an oxide film according to example embodiments can be used for various purposes. For example, the oxide film manufactured by the method of forming an oxide film according to example embodiments can be used for a dielectric layer included in a capacitor of a semiconductor memory device, a gate dielectric layer of a planar transistor, a dielectric film of a vertical NAND flash memory (flash) device, a conductive barrier layer for interconnection, a resistive layer, a magnetic layer, a liquid crystal (LC) barrier metal layer, a member for a thin-film solar cell, a member for a semiconductor device, a nanostructure, a hydrogen storage alloy, and a micro electro mechanical system (MEMS) actuator, but example embodiments of the inventive concept are not limited thereto.

[0034] Afterwards, it can be determined whether the oxide film has been formed to a desired thickness (S3). The desired thickness of the oxide film can be, for example, a set thickness, and can be set by constraints on size, or can be set to improve or optimize the functionality of the oxide film. The desired thickness can be a preset value and is related to the constraints or limitations of the processing technology, including but not limited to the aspect ratio (aspect ratio) of the substrate, time constraints, morphology constraints, and material costs. When the oxide film is formed to a thickness less than the desired thickness, the operation S2 of forming the oxide film can be repeated. When the oxide film has been formed to the desired thickness or greater, the repeated operation of forming the oxide film can be completed or interrupted.

[0035] Figure 2 is a detailed flowchart of operation S2 of forming an oxide film on the substrate 100 according to example embodiments. Figures 3A-3D 1 is a schematic conceptual diagram illustrating a mechanism for uniformly forming an oxide film on the substrate 100 .

[0036] Reference Figure 2 and 3A A first source material SM1 may be provided on a substrate 100 (S21). The first source material SM1 may be a precursor material including a first central element. The first central element may be a metal or semi-metal that forms an oxide film to be deposited.

[0037] In some example embodiments, the first source material SM1 may be obtained by ML n Here, M represents the first central element that is the central element of the first source material SM1, and L represents a ligand that binds to the central element M of the first source material SM1. In addition, n represents a number determined by the first central element M and the ligand L and is, for example, an integer in the range of 2 to 6. Since the first central element M is a metal or semimetal as described above, additional description thereof is omitted.

[0038] In some example embodiments, the first source material SM1 may be obtained by a ) n (L b ) m Indicates the material. Here, L a represents the first ligand bound to the central element M, and L b is a second ligand different from the first ligand that also binds to the first central element M. Here, n and m represent the central element M, ligand L a and ligand L b The number of decisions.

[0039] In some example embodiments, the ligand L, the first ligand L a , and the second ligand L bThe center element M can be appropriately adjusted so that the first source material SM1 has an appropriate boiling point. According to example embodiments, the ligand L, the first ligand L a , and the second ligand L b may each independently include a halogen such as fluorine (F-), chlorine (Cl-), bromine (Br-), and iodine (I-), a hydroxyl group (OH-), ammonia (NH3), a C1-C10 amine, an unsubstituted amino group (NH2-) or an amino group (NH2-) substituted with a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkyl group, a C6-C12 aryl group, a C3-C15 allyl group, a C4-C15 diene, a C5-C20 β-diketonato group, a C5-C20 β-ketimidato group, a C5-C20 β-diimidato group, or a combination thereof. For example, the ligand L, the first ligand L a , and the second ligand L b may each independently be a dimethylamino group (-N(CH3)2), an ethylmethylamino group (-NCH3C2H5), or a diethylamino group (-N(C2H5)2). However, the inventive concept is not limited thereto.

[0040] When the first source material SM1 is provided on the substrate 100, the first source material SM1 can be adsorbed on the substrate 100 in a self-limiting manner. In some example embodiments, the first source material SM1 can be chemisorbed onto the surface of the substrate 100. Although not specifically shown in FIG. 1, the bond at the surface of the substrate 100 can end in a hydroxyl group (-OH), and the hydroxyl group can react with the ligand of the first source material SM1 to form a covalent bond. Figure 3A

[0041] When the center element M of the first source material SM1 is zirconium (Zr), the first source material SM1 can include, for example, at least one of (cyclopentadienyl)tris(dimethylamino)zirconium (CpZr(NMe2)3), tetra-ethylmethylamino-zirconium (TEMAZ), tetra-diethylamino-zirconium (TDEAZ), tetra-dimethylamino-zirconium (TDMAZ), zirconium tert-butoxide (Zr(OtBu)4, abbreviated as ZTB), tetra(1-methoxy-2-methyl-2-propoxy)zirconium (Zr(mmp)4), zirconium tetrachloride (ZrCl4), ZrCp2Me2, Zr(tBuCp)2Me2, and Zr(N(iProp)2)4, but is not limited thereto.

[0042] ​When the central element M of the first source material SM1 is hafnium (Hf), the first source material SM1 can include, for example, at least one of (cyclopentadienyl)tris(dimethylamino)hafnium (CpHf(NMe2)3), hafnium tert-butoxide (Hf(OtBu)4, abbreviated as HTB), tetrakis(diethylamino)hafnium (Hf(NEt2)4, abbreviated as TDEAH), tetrakis(ethylmethylamino)hafnium (Hf(NEtMe)4, abbreviated as TEMAH), and tetrakis(dimethylamino)hafnium (Hf(NMe2)4, abbreviated as TDMAH), but is not limited thereto.

[0043] When the central element M of the first source material SM1 is yttrium (Y), the first source material SM1 can include, for example, at least one of Y(N(SiMe3)2)3, Y(N(i-Pr)2)3, Y(N(t-Bu)SiMe3)3, Y(TMPD)3, Cp3Y, (MeCp)3Y, and Y(O(i-Pr))3, but is not limited thereto.

[0044] When the central element M of the first source material SM1 is lanthanum (La), the first source material SM1 can include, for example, at least one of La(N(SiMe3)2)3, La(N(i-Pr)2)3, La(N(t-Bu)SiMe3)3, La(TMPD)3, ((i-Pr)Cp)3La, Cp3La, Cp3La(NCCH3)2, La(Me2NC2H4Cp)3, La(THD)3, and La(O(i-Pr))3, but is not limited thereto.

[0045] When the central element M of the first source material SM1 is titanium (Ti), the first source material SM1 can include, for example, at least one of tetrakis(isopropyl alcohol) titanium (Ti(O-iProp)4), titanium halide, cyclopentadienyl titanium, and bis(isopropyl alcohol) bis(2,2,6,6-tetramethyl-3,5-heptanedione) titanium (Ti(O-iProp)2(thd)2), but is not limited thereto.

[0046] When the central element M of the first source material SM1 is aluminum (Al), the first source material SM1 can include, for example, at least one of trimethylaluminum (TMA), triethylaluminum (TEA), 1-methylpyrrolidinoaluminum hydride (MPA), dimethylethylaminealuminum hydride (DMEAA), and dimethylaluminum hydride (DMAH), but is not limited thereto.

[0047] When the central element M of the first source material SM1 is germanium (Ge), the first source material SM1 can include, for example, at least one of germane (GeH4), digermane (Ge2H6), trigermane (Ge3H8), GeCl4, Ge(Me)4, and Ge(Et)4, but is not limited thereto.

[0048] When the central element M of the first source material SM1 is scandium (Sc), the first source material SM1 can include, for example, at least one of scandium chloride (ScCl3), Sc(N(i-Pr)2)3, Sc(N(t-Bu)SiMe3)3, Cp3Sc, and Sc(O(i-Pr))3, but is not limited thereto.

[0049] When the central element M of the first source material SM1 is boron (B), the first source material SM1 can include, for example, at least one of borane (BH3), diborane (B2H6), trichloroborane (BCl3), tribromoborane (BBr3), and triiodoborane (BI3), but is not limited thereto.

[0050] When the central element M of the first source material SM1 is silicon (Si), the first source material SM1 can include, for example, silane (SiH4), disilane (Si2H6), monochlorosilane (SiClH3), dichlorosilane (SiCl2H2), trichlorosilane (SiCl3H), hexachlorodisilane (Si2Cl6), diethylsilane (Et2SiH2), tetraethyl orthosilicate (Si(OCH2CH3)4, abbreviated as TEOS), or an alkylaminosilane-based compound, but is not limited thereto. The alkylaminosilane-based compound can include, for example, diisopropylaminosilane (H3Si(N(i-Pr)2)), bis(tert-butylamino)silane ((C4H9(H)N)2SiH2), tetra(dimethylamino)silane (Si(NMe2)4), tetra(ethylmethylamino)silane (Si(NEtMe)4), tetra(diethylamino)silane (Si(NEt2)4), tri(dimethylamino)silane (HSi(NMe2)3), tri(ethylmethylamino)silane (HSi(NEtMe)3), tri(diethylamino)silane (HSi(NEt2)3), bis(diethylamino)silane (H2Si(NEt2)2), bis(diisopropylamino)silane (H2Si(N(i-Pr)2)2), tri(isopropylamino)silane (HSi(N(i-Pr)2)3), or diisopropylaminosilane (H3Si(N(i-Pr)2), but is not limited thereto.

[0051] Here, Me represents methyl, Et represents ethyl, i-Pr and iProp represent isopropyl, n-Pr represents n-propyl, Bu represents butyl, n-Bu represents n-butyl, tBu and t-Bu represent tert-butyl, Cp represents cyclopentadienyl, THD represents 2,2,6,6-tetramethyl-3,5-heptanedionato, TMPD represents 2,2,6,6-tetramethyl-p-phenylenediaminato, acac represents acetylacetonato, hfac represents hexafluoroacetylacetonato, and FOD represents 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato.

[0052] With reference to Figure 2 and 3B The electron donor compound ED can be provided onto the substrate 100 (S22).

[0053] The electron donor compound ED can be a compound having an unshared electron pair or including a double bond or a triple bond. In some example embodiments, the electron donor compound ED can be an oxygen-containing, nitrogen-containing, sulfur-containing, or phosphorus-containing hydrocarbon compound having an unshared electron pair. In some example embodiments, the electron donor compound ED can include at least one of a C1-C10 alcohol compound, a C2-C10 ether compound, a C3-C10 ketone compound, a C6-C12 aryl compound, a C3-C15 allyl compound, a C4-C15 diene compound, a C5-C20 β-diketone compound, a C5-C20 β-ketimine compound, a C5-C20 β-diimine compound, ammonia, a C1-C10 amine compound, a C1-C10 thiol compound, and a C2-C10 sulfide compound.

[0054] The electron donor compound ED can be combined with the first source material SM1. For example, the electron donor compound ED can be physically adsorbed on the first source material SM1. That is, the electron donor compound ED can provide an unshared electron pair or a shared electron pair to a first center element of the first source material SM1 and form a van der Waals bond. The van der Waals bond has a weaker binding force than a covalent bond and can have a binding energy of about 0.5 eV or less per adsorbed species. When the electron donor compound ED provides an electron to the first center element, intermolecular forces can occur between the first source material SM1 and the electron donor compound ED. The intermolecular forces between the first source material SM1 and the electron donor compound ED can be weaker than the binding force between the first center element and a ligand in the first source material SM1.

[0055] In Figures 3A-3D , a solid line represents a covalent bond or chemisorption, and a dashed line represents a van der Waals bond or physisorption.

[0056] The excess electron donor compound ED can be purged and / or removed, for example, by supplying a non-reactive gas to the substrate 100. The excess electron donor compound ED can include electron donor compounds ED that are not bound to the first source material SM1.

[0057] Referring to Figure 2 and 3C The second source material SM2 can be provided on the substrate 100 (S23).

[0058] The second source material SM2 can be a material represented by M'(L n Here, M' represents a second central element that is a central element of the second source material SM2, and L represents a ligand that is bound to the M' that is the central element of the second source material SM2. Further, n represents a number determined by the second central element M' and the ligand L and is, for example, an integer in the range of 2-6. Since the second central element M' is a metal or a semimetal as described above, additional description thereof will be omitted.

[0059] In some example embodiments, the second source material SM2 can be a material represented by M'(L a ) n (L b ) m Here, L a represents a first ligand bonded to the second central element M', and L b represents a second ligand that is bound to the second central element M' and is different from the first ligand. Here, n and m represent numbers determined by the second central element M', the ligand L a , and the ligand L b .

[0060] Since the ligand L, the first ligand L a , and the second ligand L b have been described in detail in the description of the first source material SM1, additional description thereof will be omitted. However, the ligand L, the first ligand L a , and the second ligand L b in the first source material SM1 can be independently different from the ligand L, the first ligand L a , and the second ligand L b in the second source material SM2.

[0061] The second source material SM2 can be chemisorbed on the substrate 100 and does not form a bond with the first source material SM1. When the electron donor compound ED is not bound to the first source material SM1, the first source material SM1 can react with the second source material SM2, which can produce reactions and compounds that are not intended for deposition of the oxide film. The following Chemical Equations 1 and 2 show examples of unintended reactions of the two source materials.

[0062] CpZr(NMe2)3 + HSi(NMe2)3 → CpZr(NMe2)2(H) + Si(NMe2)4 (1).

[0063] SiH4 + 4BC13→ 3SiCl4 + 4BH3 (2).

[0064] CpZr(NMe2)2(H) produced by the reaction of the source material in Chemical Equation 1 and BH3 produced in Chemical Equation 2 can have poor thermal stability, and Si(NMe2)4 can be produced in a solid state and form particles. Thus, these unwanted reaction products can become an obstacle to the formation of an oxide film having a desired thickness at a desired location.

[0065] However, in the present disclosure, the electron-donating compound ED can bind to the first source material SM1 and prevent the first source material SM1 from reacting with the second source material SM2, and thus, the uniformity of the deposited oxide film can be improved.

[0066] When the second source material SM2 is provided on the substrate 100, the second source material SM2 can be adsorbed on the substrate 100 in a self-limiting manner. In some example embodiments, the second source material SM2 can be chemisorbed on the surface of the substrate 100. Although Figure 3C Although not specifically shown in FIG. 1, in some example embodiments, the bond at the surface of the substrate 100 can end in a hydroxyl group (-OH), and the hydroxyl group can react with a ligand of the second source material SM2 to form a covalent bond.

[0067] Referring to Figure 2 and 3D An oxidizing agent can be provided on the substrate 100 (S24).

[0068] In some example embodiments, the oxidizing agent can include at least one of H2O, O2, O3, N2O, NO, NO2, N2O4, H2O2, C1-C10 alcohol, C2-C10 ether, C3-C10 ketone, C1-C10 carboxylic acid, and C1-C10 ester.

[0069] The electron-donating compound ED can include carbon and hydrogen as main constituent elements. When the oxidizing agent is provided on the substrate 100, the carbon in the electron-donating compound ED can react with the oxidizing agent, for example, with oxygen, and the oxidized electron-donating compound can be more easily removed. In addition, since the ligands of the first source material SM1 and the second source material SM2 also include carbon and hydrogen as main constituent elements, the ligands can also react with the oxidizing agent and be more easily removed.

[0070] The first central element M and the second central element M' can together react with oxygen (inFigure 3D oxide film 100NL is formed on the substrate 100. It can be determined whether the oxide film 100NL has been formed to a desired thickness (refer to Figure 1 S3 in FIG. 6). When the thickness of the oxide film 100NL is less than the desired thickness, the above-described cycle can be repeated. Further, the oxide film 100NL including the first central element M and the second central element M ′ together with the substrate 100 can serve as the substrate 100N for the next cycle.

[0071] Figure 4 is a schematic view of a semiconductor apparatus 1 configured to perform a method of forming a material film according to an example embodiment.

[0072] Referring to Figure 4 , the semiconductor processing apparatus 1 can include a process material supply system 20a capable of independently supplying the electron donor compound 14, the first source material 16, the second source material 17, the purge gas 19, and the oxidizing agent 18 into the reaction chamber 10. The process material supply system 20a can be configured to independently supply the electron donor compound 14, the first source material 16, the second source material 17, the purge gas 19, and the oxidizing agent 18 into the reaction chamber 10 at different times for the same or different periods of time. Alternatively, the process material supply system 20a can be configured to simultaneously supply at least two of the electron donor compound 14, the first source material 16, the second source material 17, the purge gas 19, and the oxidizing agent 18 into the reaction chamber 10. The reaction chamber 10 can be a chamber into which the substrate 100 can be loaded and unloaded.

[0073] The semiconductor processing apparatus 1 can be controlled by a controller (not shown). The controller can include a memory functionally connected to a processor. The processor can include processing circuitry such as hardware including logic circuits; a hardware / software combination such as a processor executing software; or a combination thereof. For example, the processing circuitry can more particularly include, but is not limited to, a central processing unit (CPU), an arithmetic logic unit (ALU), a digital signal processor, a microcomputer, a field programmable gate array (FPGA), a programmable logic unit, a microprocessor, an application specific integrated circuit (ASIC), etc.

[0074] The process material supply system 20a can include a first source material supply apparatus 30a, a second source material supply apparatus 30b, an electron donor compound supply apparatus 60a, a purge gas supply apparatus 90a, and an oxidizing agent supply apparatus 80a. The first source material supply apparatus 30a can be an apparatus configured to supply the first source material 16 into the reaction chamber 10. The second source material supply apparatus 30b can be an apparatus configured to supply the second source material 17 into the reaction chamber 10.

[0075] The first and second source material supply devices 30a and 30b may include source material storage containers 40 and 41 and vaporizers (evaporators) 50 and 51. The source material storage containers 40 and 41 may be connected to the vaporizers 50 and 51 via conduits 42 and 43, respectively. The conduits 42 and 43 may include flow rate control devices 44 and 45, respectively. The vaporizers 50 and 51 may be connected to the reaction chamber 10 via conduits 52 and 53, respectively, and the conduits 52 and 53 may include flow rate control devices 54 and 55, respectively. The vaporizers 50 and 51 may be, for example, atomizers.

[0076] The first and second source materials 16 and 17 in the first and second source material storage containers 40 and 41 may be respectively transferred to the vaporizers 50 and 51 and vaporized in the vaporizers 50 and 51. For example, the vaporizers 50 and 51 may vaporize the first and second source materials 16 and 17 using pressure (e.g., an atomizer) or heat. The first and second source materials 16 and 17 vaporized by the vaporizers 50 and 51 may be supplied to the reaction chamber 10.

[0077] The electron donor compound supply device 60a may be a device configured to supply the electron donor compound 14 into the reaction chamber 10. The electron donor compound 14 may be stored in the electron donor compound supply device 60a and supplied from the electron donor compound supply device 60a to the reaction chamber 10 through the conduit 62.

[0078] The electron donor compound supply device 60 a may be connected to the reaction chamber 10 via a conduit 62 , and the conduit 62 may include a flow rate control device 64 capable of controlling the flow rate of the electron donor compound 14 .

[0079] The oxidant supply device 80a may be a device configured to supply the oxidant 18 into the reaction chamber 10. The oxidant 18 may be stored in the oxidant supply device 80a and supplied from the oxidant supply device 80a to the reaction chamber 10 through a conduit 82. The oxidant supply device 80a may be connected to the reaction chamber 10 through the conduit 82, and the conduit 82 may include a flow rate control device 84 capable of controlling the flow rate of the oxidant 18. Although not shown, when the oxidant 18 is not supplied as a gas, a vaporizer may be used to vaporize the oxidant 18, and the vaporized oxidant 18 may be supplied to the reaction chamber 10, or a non-gaseous oxidant 18 may be supplied to the reaction chamber 10 as, for example, a liquid.

[0080] Purge gas supply device 90a may be a device configured to supply purge gas 19 into reaction chamber 10. Purge gas 19 may be stored in purge gas supply device 90a and supplied from purge gas supply device 90a into reaction chamber 10 through conduit 92. Purge gas supply device 90a may be connected to reaction chamber 10 through conduit 92, and conduit 92 may include a flow rate control device 94 capable of controlling the flow rate of purge gas 19.

[0081] The conduits 42, 52, 43, 53, 62, 82, and 92 can be conduits through which fluids can flow, and the flow rate control devices 44, 54, 45, 55, 64, 65, 84, and 94 can include valve systems capable of controlling the flow (flow rate) of the respective fluids and gases.

[0082] The process material supply system 20a can be a system capable of independently supplying the electron donor compound 14, the first source material 16, the second source material 17, the purge gas 19, and the oxidizing agent 18 into the reaction chamber 10. The process material supply system 20a can be configured to supply the electron donor compound 14, the first source material 16, the second source material 17, the purge gas 19, and the oxidizing agent 18 into the reaction chamber 10 at different times for the same or different periods of time or simultaneously.

[0083] By using the method according to the example embodiment, a high aspect ratio material film including at least two non-oxygen elements can be formed to have uniformity in composition and size.

[0084] Referring to Figure 4 The electron donor compound supply apparatus 60a can be an apparatus configured to supply the electron donor compound 14 into the reaction chamber 10. The electron donor compound supply apparatus 60a can include a canister configured to supply the electron donor compound 14. The canister can be configured to uniformly supply the electron donor compound 14.

[0085] The electron donor compound supply apparatus 60a can supply the electron donor compound 14 in a liquid state into the flow rate control device 64. The flow rate of the electron donor compound 14 can be constantly controlled by the flow rate control device 64, and then the electron donor compound 14 can be vaporized by the vaporizer 70a, and then the flow rate of the vaporized electron donor compound 14 can be controlled by the flow rate control device 65. Accordingly, the amount of the electron donor compound 14 supplied into the reaction chamber 10 can be uniformly controlled.

[0086] The electron donor compound 14, the first source material 16, the second source material 17, and the oxidizing agent 18 can each be transported using a carrier gas. The carrier gas can be an inert gas such as argon (Ar), helium (He), nitrogen (N2), or neon (Ne), but is not limited thereto. The flow rate of the carrier gas can be selected based on factors such as the deposition rate of the oxide film, the vapor pressure of the material to be transported, and the temperature. For example, the flow rate of the carrier gas can range from about 200 standard cubic centimeters per minute (seem) to about 1300 seem.

[0087] Figures 5A-5FTo illustrate the timing of the supply cycle of the first source material SM1, the second source material SM2, the electron donor compound ED, and the oxidizing agent according to the example embodiment, a timing chart of the configuration is shown in FIG. 10. In Figures 5A-5F each of the feed materials can be supplied in pulses. The flow rate and the feed time of each feed material can not be proportional to the height and the width of the pulses shown in Figures 5A-5F Although Figures 5A-5F not specifically shown in

[0088] Referring to Figure 5A , after the first source material SM1 is supplied onto the substrate 100, the electron donor compound ED can be supplied, and the second source material SM2 can be subsequently supplied.

[0089] When the first source material SM1 is initially supplied, the first source material SM1 can chemisorb on the surface of the substrate 100, and due to the purge process, the first source material SM1 can form at one molecular layer or less.

[0090] After the electron donor compound ED is supplied, the electron donor compound ED can physisorb on the first source material SM1. As described above, the electron donor compound ED can form a van der Waals bond while providing an unshared electron pair or a shared electron pair to the first source material SM1.

[0091] After that, the excess electron donor compound ED can be purged or removed, for example, with the purge gas 19.

[0092] Subsequently, the second source material SM2 can be supplied onto the substrate 100. The second source material SM2 can chemisorb on the substrate 100 without reacting with the first source material SM1. As described above, since the first source material SM1 is bound to the electron donor compound ED, the first source material SM1 can be prevented from reacting with the second source material SM2. Therefore, non-uniform film growth and particle generation due to the reaction of the first source material SM1 with the second source material SM2 can be minimized, suppressed, or prevented.

[0093] After that, when the oxidizing agent is supplied into the reaction chamber, the oxidizing agent can react with the first central element M and the second central element M' to form an oxide film having a composition of approximately MxM'yOz. Due to the reaction with the oxidizing agent, the electron donor compound ED can be removed from the surface of the substrate 100.

[0094] When the reaction chamber is purged with a purge gas, the excess oxidizing agent and the reaction byproducts can be removed from the reaction chamber.

[0095] Referring to Figure 5B, the supply cycle is basically the same as that shown in Figure 5A , except that the electron-donor compound ED is supplied before the first source material SM1 is supplied on the substrate 100. Thus, the differences between the supply cycles shown in Figure 5A and 5B will be mainly described, and the repetitive description will be omitted.

[0096] When the electron-donor compound ED is supplied onto the substrate 100, the electron-donor compound ED can be physically adsorbed on the surface of the substrate 100 to form a monolayer. The monolayer of the electron-donor compound ED can have an effect of preventing and delaying the chemical adsorption of the subsequent first source material SM1.

[0097] When the surface of the feature on which the oxide film will be formed (i.e., the substrate 100) has a high aspect ratio, the chemical adsorption of the first source material SM1 can occur unevenly from the upstream side of the mass transfer to the downstream side of the mass transfer. Here, the term "upstream" refers to the upstream side of the flow of the material to be deposited, and the term "downstream" refers to the downstream side of the flow of the material to be deposited. However, in the present example embodiment, the chemical adsorption of the first source material SM1 on the surface of the feature (i.e., the surface of the substrate 100) can be slowed down due to the previously physically adsorbed electron-donor compound ED. Thus, the first source material SM1 can further diffuse to the downstream side, and the overall uniformity of the first source material SM1 can be improved.

[0098] Referring to Figure 5C , the supply cycle is basically the same as that shown in Figure 5A , except that the supply cycle further includes supplying the electron-donor compound ED after the second source material SM2 is provided on the substrate 100 and before the oxidizing agent is provided. Thus, the differences between the supply cycles shown in Figure 5A and 5C will be mainly described, and the repetitive description will be omitted.

[0099] When the first source material SM1 and the electron-donor compound ED are sequentially supplied into the reaction chamber, the first source material SM1 can be chemically adsorbed on the substrate 100, and the electron-donor compound ED can be physically adsorbed thereon. Here, when the second source material SM2 is supplied into the reaction chamber, the second source material SM2 can be chemically adsorbed on the substrate 100, and excess second source material SM2 can additionally be physically adsorbed thereon. The physically adsorbed second source material SM2 as described above can be partially removed using a purge process, but a portion of the second source material SM2 can still remain. The excess adsorbed physically adsorbed second source material SM2 can need to be removed to form a uniform oxide film.

[0100] Subsequently, when the electron donor compound ED is supplied, the electron donor compound ED can be van der Waals-bonded with the second source material SM2. For example, when the electron donor compound is an ether-based material, the unshared electron pair of the oxygen atom contained in the ether group can be bonded with the central atom of the excess-adsorbed second source material SM2. The second source material SM2 physically adsorbed on the other second source material SM2 can be released due to the bonding, and the excess-adsorbed second source material SM2 can be mostly removed. When the reaction chamber is subsequently purged again with the purge gas, the excess electron donor compound ED and reaction by-products can be removed from the reaction chamber, and a layer of the second source material SM2 chemically adsorbed at a level of one monolayer or less can be obtained on the substrate 100.

[0101] After that, when the oxidizing agent is supplied, the oxidizing agent can form an oxide film as described with reference to Figure 5A Subsequently, the reaction chamber can be purged with a purge gas and thus, the excess oxidizing agent and reaction by-products can be removed from the reaction chamber.

[0102] With reference to Figure 5D , the supply cycle can be substantially the same as the supply cycle shown in Figure 5C except that the electron donor compound ED is supplied before the first source material SM1 is supplied onto the substrate 100. Therefore, the difference between the supply cycles shown in Figure 5C and 5D will be mainly described, and the repeated description will be omitted.

[0103] However, Figure 5D the supply cycle shown in Figure 5B may be similar to the supply cycle shown in Figure 5D because the electron donor compound ED is supplied before the first source material SM1 is supplied onto the substrate 100, and thus Figure 5B the supply cycle shown in may have a similar effect to the supply cycle shown in

[0104] . In particular, a monolayer of the electron donor compound ED can have an effect of inhibiting and delaying the subsequent chemical adsorption of the first source material SM1, and the first source material SM1 can further diffuse to the downstream side over the surface on which the feature of the oxide film will be formed (i.e., the surface of the substrate 100). Therefore, the uniformity of the first source material SM1 can be improved on the surface on which the feature of the oxide film will be formed.

[0105] In summary, an oxide having an extremely excellent or substantially uniform step coverage can be formed on the surface of the feature (e.g., the surface of the substrate 100).

[0106] Referring to Figure 5E , the period during which the electron donor compound ED is supplied can overlap the period during which the first source material SM1 is supplied by a predetermined time OL. In particular, the time point at which the supply of the electron donor compound ED is started can be earlier than the time point at which the supply of the first source material SM1 is started. Further, the time point at which the supply of the electron donor compound ED is ended can be later than the time point at which the supply of the first source material SM1 is ended. That is, the period during which the first source material SM1 is supplied can be nested in the period during which the electron donor compound ED is supplied.

[0107] When the supply cycle is configured as shown in Figure 5E , effects similar to those of the example embodiment shown in Figure 5B can be obtained. However, compared to the example embodiment of Figure 5B , the purge time between the first pulse of the electron donor compound ED and the pulse of the first source material SM1 and the purge time between the pulse of the first source material SM1 and the second pulse of the electron donor compound ED can be reduced, and thus, the oxide film can be formed quickly.

[0108] In some cases, the first source material SM1 can bind to each other to form a dimer or a trimer. When the dimer or the trimer is adsorbed on the surface of the substrate 100, the first source material SM1 can be adsorbed in at least two layers to cause excessive adsorption. In this case, when the period during which the first source material SM1 is supplied overlaps the period during which the electron donor compound ED is supplied, the possibility that the first source material SM1 will form a dimer or a trimer can be reduced, thereby mitigating the problem of excessive adsorption.

[0109] Referring to Figure 5F , the supply cycle can be configured such that the supply of the electron donor compound ED into the reaction chamber precedes the supply of the first source material SM1 into the reaction chamber.

[0110] In this case, the electron donor compound ED can be adsorbed on the surface of the feature and have the effects of stabilizing the surface of the feature and inhibiting and delaying the subsequent chemical adsorption of the first source material SM1. The first source material SM1 can further diffuse to the downstream side above the surface of the feature (i.e., the surface of the substrate 100) on which the oxide film is to be formed. Thus, on the surface of the feature on which the oxide film is to be formed, the uniformity of the first source material SM1 can be improved. Since the electron donor compound ED is adsorbed on the surface of the feature, the electron donor compound ED can also inhibit the chemical adsorption of the second source material SM2.

[0111] Afterwards, when an oxidizing agent is supplied, the oxidizing agent can form an oxide film, as described with reference to Figure 5A When the reaction chamber is then purged with a purge gas, excess oxidizing agent and reaction byproducts can be removed from the reaction chamber.

[0112] With reference to Figures 5A-5F The embodiments described are example embodiments, and it is clear that not only Figures 5A-5F combinations of the embodiments, but also supply cycles that can be readily implemented by one skilled in the art based on the embodiments described, fall within the scope of the inventive concept. Figures 5A-5F

[0113] Figures 6A-6H is a process sequence of a method of manufacturing a semiconductor device according to an example embodiment.

[0114] With reference to Figure 6A An interlayer insulating film 211, a contact plug 212, and an etching stop film 213 can be formed on the substrate 210, and a first mold film 214 for forming a capacitor can be formed thereon. A support layer 232L can be formed on the first mold film 214. In some example embodiments, the support layer 232L can have a thickness of about 10 nm to about 500 nm. A mask pattern 240 for patterning the support layer can be formed on the support layer 232L. The mask pattern 240 can be formed to have a pattern corresponding to a support pattern to be subsequently formed. The mask pattern 240 can be, for example, a photoresist pattern.

[0115] The substrate 210 can be a semiconductor substrate such as a silicon substrate, a germanium substrate, or a silicon-germanium substrate. However, the substrate 210 is not limited thereto and can be any of the substrates described above with reference to Figure 1 and 2 The substrate 210 can be a semiconductor substrate such as a silicon substrate, a germanium substrate, or a silicon-germanium substrate. However, the substrate 210 is not limited thereto and can be any of the substrates described above with reference to

[0116] The interlayer insulating film 211 can include a dielectric material. For example, the interlayer insulating film 211 can include an oxide, a nitride, and / or an oxynitride. The interlayer insulating film 211 can include a single layer or include at least two layers.

[0117] The contact plug 212 can be formed on the substrate 210 and through the interlayer insulating film 211. The contact plug 212 can include at least one of a semiconductor material such as doped polysilicon (poly-Si), a metal such as tungsten (W), titanium (Ti), tantalum (Ta), copper (Cu), and aluminum (Al), a metal nitride such as tungsten nitride (WN), titanium nitride (TiN), and tantalum nitride (TaN), a metal silicon nitride such as titanium silicon nitride (TiSiN) and tungsten silicon nitride (WSiN), and a metal silicide such as tungsten silicide (WSi).

[0118] ​Although not shown in the drawings, a plurality of word lines and a plurality of bit lines can be formed on the substrate 210, cross each other, and be covered with the interlayer insulating film 211. Doped regions can be provided in the substrate 210 on both sides of each of the word lines, and each of the contact plugs 212 can be connected to one of the doped regions. Further, the contact plugs 212 can be electrically connected to the switching elements corresponding thereto. The switching elements can be active elements such as transistors or diodes.

[0119] The first mold film 214 can be formed on the etching stop film 213. The first mold film 214 can include at least one of an oxide film, a nitride film, and an oxynitride film.

[0120] Although not shown, a buffer film (not shown) can be further formed between the first mold film 214 and the etching stop film 213. The buffer film can include at least one of an oxide film and a nitride film.

[0121] The support layer 232L can include a material having etching selectivity with respect to the first mold film 214. For example, when the first mold film 214 is partially or entirely removed using a low ammonium fluoride liquid (LAL) lift-off process, the support layer 232L can include a dielectric material having a relatively low etching rate with respect to the LAL.

[0122] When the first mold film 214 includes at least one of SiO2, SiGe, Si, and a carbon-based material, the support layer 232L can be formed using any one selected from the group consisting of SiN, SiCN, TaO, and TiO2. However, the inventive concept is not limited to these materials.

[0123] Referring to Figure 6B The exposed portions of the support layer 232L can be anisotropically etched using the mask pattern 240 as an etching mask, thereby forming a support layer pattern 232P. Due to the anisotropic etching process, portions of the first mold film 214 can be exposed between the support layer pattern 232P.

[0124] Referring to Figure 6CA second mold film 215 can be formed on the first mold film 214 and the support layer pattern 232P. The second mold film 215 can include the same material as the first mold film 214 or a material having an etching rate similar to that of the first mold film 214. For example, when the first mold film 214 and the second mold film 215 are removed using an LAL lift-off process, the second mold film 215 can include a material having an etching rate for LAL that differs by 10% or less from the etching rate for LAL of the first mold film 214. The second mold film 215 can be formed to a thickness that completely covers the support layer pattern 232P. For example, the second mold film 215 can be formed to a thickness of at least 50 nm. Further, the sum of the thicknesses of the first mold film 214 and the second mold film 215 can range from about 50 nm to about 200 nm. - about 50 nm

[0125] Referring to Figure 6D The second mold film 215, the support pattern 232, the first mold film 214, and the etching stop film 213 can be etched so that the contact plug 212 is exposed at locations where the cylindrical lower electrode is to be formed, thereby forming a plurality of openings H. One opening H can be connected to at least one of the other openings H through the support pattern 232. However, the opening H can not necessarily be connected to at least one of the other openings H.

[0126] The openings H can expose the upper surface of the contact plug 212. The formation of the openings H can include forming a mask pattern for defining the openings H on the second mold film 215 and etching the second mold film 215, the support pattern 232, and the first mold film 214 using the mask pattern as an etching mask. According to an example embodiment, the openings H can be formed in a hole shape.

[0127] Referring to Figure 6E A conductive material can be deposited on the entire surface of the structure formed on the substrate 210. That is, for example, the conductive material can be deposited on the inner walls of the openings H and the second mold film 215, and the conductive material deposited on the inner walls of the openings H can be separated to form a plurality of lower electrodes 220. The formation of the lower electrodes 220 can include conformally forming the conductive material, forming a fill layer (not shown) on the entire surface of the resulting structure formed on the substrate 210 to fill the openings H, and performing a planarization process by using an etch-back process and / or a chemical mechanical polishing (CMP) process to remove the fill layer and the conductive material so that the second mold film 215 is exposed. The lower electrodes 220 can be electrically connected to the contact plug 212. According to an example embodiment, the lower electrodes 220 can include a plate (sheet) portion in contact with the contact plug 212 and a sidewall portion extending in a vertical direction from an edge of the plate portion. Thus, the lower electrodes 220 can have an empty space defined by the plate portion and the sidewall portion. For example, the lower electrodes 220 can be cylindrical.

[0128] The lower electrode 220 can include, for example, a semiconductor material such as doped polysilicon; a metal such as ruthenium (Ru), iridium (Ir), titanium (Ti), and / or tantalum (Ta); a conductive metal nitride such as titanium nitride (TiN), tantalum nitride (TaN), and tungsten nitride (WN); a conductive metal oxide such as iridium oxide (IrO); and / or a composite material thereof. The lower electrode 220 can include a single layer or a multi-layer structure.

[0129] The conductive material on the second resist film 215 can be removed using a CMP process, and the filling layer can be removed using an etch-back process. The filling layer can include the same material as the first resist film 214 and / or the second resist film 215 or a material having an etching rate similar to that of the first resist film 214 and / or the second resist film 215. The filling layer can be, for example, an oxide film.

[0130] Although an example in which the lower electrode 220 is a cylindrical shape (i.e., a single cylindrical storage (OCS) type) is described, those skilled in the art will understand that the following processes can also be applied to a columnar lower electrode or a concave lower electrode.

[0131] Referring to Figure 6F After the lower electrode 220 is formed, the first resist film 214 and the second resist film 215 can be removed. In addition, the filling layer can be removed together with the first resist film 214 and the second resist film 215 or separately. For example, the first resist film 214, the second resist film 215, and the filling layer can be removed by a lift-off process using LAL including ammonium fluoride (NH4F), hydrofluoric acid (HF), and water, or can be removed by using HF. Accordingly, as described above, the material of the support layer pattern 232P can be selected to have a lower etching rate than the first resist film 214 and the second resist film 215 with respect to LAL. At least a portion of the lower electrode 220 can be supported by the support pattern 232. In Figure 6F In the embodiment, the support pattern 232 can be formed at a level lower than the end portion of the cylindrical structure (i.e., the lower electrode 220 of the cylindrical type). In some example embodiments, the support pattern 232 can be formed at the same level as the end portion of the lower electrode 220.

[0132] Referring to Figure 6G After the first resist film 214, the second resist film 215, and the filling layer are removed, a capacitor dielectric film 222 can be formed conformally on the lower electrode 220. The capacitor dielectric film 222 can include, for example, a metal oxide and / or a semi-metal oxide formed using the method described with reference to Figure 2 and 3A -3D. Hereinafter, the metal oxide and / or the semi-metal oxide will be referred to as a metal oxide. Figure 7 and8A -8E further describes the method of manufacturing the capacitor dielectric film 222 in detail. Figure 7 A flowchart of the method of forming the oxide film according to the example embodiment is illustrated. Figures 8A-8E A conceptual diagram of the corresponding operation of the process of forming the oxide film on the lower electrode 220 is illustrated. Figure 6G A conceptual diagram of the corresponding operation of the process of forming the oxide film on the lower electrode 220 is illustrated.

[0133] Referring to Figure 7 First, the substrate 210 on which the lower electrode 220 is formed can be loaded into the reaction chamber (S1). Since the loading of the substrate 210 into the reaction chamber is described with reference to Figure 1 , a detailed description thereof will be omitted.

[0134] Referring to Figure 7 and 8A , the electron donor compound ED can be supplied onto the surface of the lower electrode 220 (S1a). Here, since the object on which the oxide film is to be formed is the lower electrode 220, the lower electrode 220 can serve as the substrate.

[0135] The electron donor compound ED can be adsorbed on the surface of the lower electrode 220. In particular, the electron donor compound ED can be physically adsorbed on the surface of the lower electrode 220. In some example embodiments, the electron donor compound ED can be bound to the material of the lower electrode 220 due to van der Waals attraction.

[0136] In some example embodiments, the top end T of the lower electrode 220 can be more favorable in terms of mass transfer than the bottom end B thereof. In this case, the density of the electron donor compound ED adsorbed on the top end T of the lower electrode 220 can be higher than the density of the electron donor compound ED adsorbed on the bottom end B of the lower electrode 220. In further example embodiments, although the top end T of the lower electrode 220 can be upstream in terms of mass transfer than the bottom end B of the lower electrode 220, when the rate-controlling step is a step (e.g., the adsorption step) other than the diffusion step, the density of the electron donor compound ED adsorbed on the top end T of the lower electrode 220 can be substantially equal to the density of the electron donor compound ED adsorbed on the bottom end B of the lower electrode 220.

[0137] Referring to Figure 2 , 7 and 8B, the first source material SM1 can be provided on the lower electrode 220.

[0138] The first source material SM1 can be chemisorbed on the surface of the lower electrode 220. Also, the electron donor compound ED can be physisorbed on the lower electrode 220 as described above, and the adsorption of the first source material SM1 can be inhibited to some extent due to the volume of the adsorbed electron donor compound ED. Thus, the adsorption rate of the first source material SM1 at the top end T of the lower electrode 220 can be slowed down, and the possibility of the first source material SM1 diffusing to the bottom end B of the first source material SM1 can increase. As a result, the uniformity of the first source material SM1 adsorbed on the lower electrode 220 can be significantly improved compared to the case where the electron donor compound ED is not previously physisorbed.

[0139] Referring to Figure 2 , 7 and 8C, the electron donor compound ED can be provided to bind with the first source material SM1.

[0140] The electron donor compound ED supplied during the current operation can be selected to be van der Waals bound with the first source material SM1. Since the electron donor compound ED has been described above, a detailed description thereof will be omitted.

[0141] Since the first source material SM1 is van der Waals bound with the electron donor compound ED, the first source material SM1 can be prevented from being bound with the second source material SM2 that is subsequently supplied. That is, when the first source material SM1 is brought into contact with the second source material SM2, the ligands of the first and second source materials SM1 and SM2 can react with each other in the absence of the electron donor compound to produce unintended reaction products. The unintended reaction products can become an obstacle to the formation of a uniform oxide film. However, when the first source material SM1 remains bound with the electron donor compound ED, even if the first source material SM1 is brought into contact with the second source material SM2, the first source material SM1 can not react with the second source material SM2, and the second source material SM2 can be adsorbed on the lower electrode 220, as will be described in further detail below.

[0142] Referring to Figure 2 , 7 and 8D, the second source material SM2 can be supplied onto the lower electrode 220. The second source material SM2 supplied onto the lower electrode 200 can be chemisorbed on the surface of the lower electrode 200.

[0143] Meanwhile, as described above, when the second source material SM2 comes into contact with the first source material SM1, side reactions may result in the formation of products that are difficult to decompose or purge. These products may accumulate near the upstream end of the structure with a high aspect ratio, thereby inhibiting the formation of a uniform oxide film. However, when the first source material SM1 is combined with the electron donor compound ED van der Waals, as described above, side reactions may be prevented or may not occur even when the first source material SM1 and the second source material SM2 are brought into contact.

[0144] Therefore, since the reaction between the second source material SM2 and the first source material SM1 can be reduced or prevented, the chance that the second source material SM2 will be adsorbed on the surface of the lower electrode 220 and diffuse to the downstream side can be increased, and the second source material SM2 can be uniformly chemically adsorbed on the lower electrode 220.

[0145] exist Figure 8D In the lower electrode 220 shown in FIG, since the substrate is located below the lower electrode 220 and the deposited material is transferred from the upper side to the lower side, the top end T of the lower electrode 220 can be referred to as upstream, and the bottom end B of the lower electrode 220 can be referred to as downstream.

[0146] Reference Figure 2 、 7 and 8E, an oxidant may be supplied to the lower electrode 220. The oxidant may remove the electron donor compound ED adsorbed on the lower electrode 220 and the electron donor compound ED adsorbed on the first source material SM1. For example, since the electron donor compound ED includes carbon as a main component, the electron donor compound ED may react with oxygen of the oxidant and be easily removed.

[0147] In addition, the ligands of the first source material SM1 and the second source material SM2 may also be removed due to the oxide, and the first central element SM1e and the second central element SM2e may react with oxygen to form a material film having a composition of MxM'yOz. Figure 8E Detailed illustration of oxygen (O) is omitted.

[0148] As reference Figure 2 and 3A- As described in 3D, the cycle including the above process can be repeated multiple times, and thus, the capacitor dielectric film 222 having a desired thickness can be obtained. For example, the first source material, the electron donor compound, and the second source material can be deposited by atomic layer deposition (ALD), and the deposition of the first and second source materials, the electron donor compound, and the oxidizing agent can be considered as a part of one atomic layer deposition (ALD) cycle, in which the ALD cycle can be performed multiple times to reach a desired thickness for the oxide layer. Here, the desired thickness of the capacitor dielectric film can be determined by the diameter of the opening H, and be a percentage of the inner diameter of the opening H, but example embodiments are not limited thereto.

[0149] Figure 9A To schematically illustrate the concentration C2 of the first central element SM1e and the concentration C1 of the second central element SM2e with respect to the z-axis position in the capacitor dielectric film 222 of Figure 8E , the graph of the concentration C2 of the first central element SM1e and the concentration C1 of the second central element SM2e with respect to the z-axis position in the capacitor dielectric film 222 of Figure 9A , it can be seen that the concentration C2 of the first central element SM1e and the concentration C1 of the second central element SM2e are substantially constant regardless of the z-axis position. Thus, the ratio C2 / C1 of the concentration C2 of the first central element SM1e to the concentration C1 of the second central element SM2e can also be almost constant. In some example embodiments, the percentage variation of the concentration ratio C2 / C1 according to the position can be in the range of about -15% to about +15%.

[0150] In addition, the thickness of the capacitor dielectric film 222 can be almost constant regardless of the position, and a step coverage of about 95% or more, about 98% or more, or about 99% or more can be achieved.

[0151] Figure 9B To schematically illustrate the concentration of the first central element SM1e and the concentration of the second central element SM2e with respect to the z-axis position in the capacitor dielectric film 222 when the operation of adsorbing the electron donor compound ED on the first source material SM1 is omitted. Specifically, Figure 9B the graph of the concentration of the first central element SM1e and the concentration of the second central element SM2e with respect to the z-axis position in the capacitor dielectric film 222 is obtained in a case where, after the first source material SM1 is adsorbed on the surface of the lower electrode 220, the operation of adsorbing the electron donor compound ED on the first source material SM1 is omitted, and the second source material SM2 is directly supplied.

[0152] Referring to Figure 9B , the concentrations of the first central element SM1e and the second central element SM2e can gradually increase toward the upstream side, while the concentrations of the first central element SM1e and the second central element SM2e can gradually decrease away from the upstream side.

[0153] In addition, the ratio of the first central element SM1e and the second central element SM2e may vary according to the z-axis position, and thus, it may be difficult to control dispersion, and electrical properties of the semiconductor device may be non-uniform.

[0154] Reference Figure 6H , an upper electrode 224 may be formed on the capacitor dielectric film 222, thereby forming a capacitor. The upper electrode 224 may include, for example, a semiconductor material such as doped polycrystalline Si; a metal such as ruthenium (Ru), iridium (Ir), titanium (Ti), and / or tantalum (Ta); a conductive metal nitride such as titanium nitride (TiN), tantalum nitride (TaN), and tungsten nitride (WN); a conductive metal oxide such as iridium oxide (IrO); and / or a composite thereof. The upper electrode 224 may include a single layer or a stacked structure of at least two layers.

[0155] The aspect ratio AR of the lower electrode 220 may be defined by Equation 1:

[0156] AR=c / min(a,b)(1),

[0157] Wherein a represents the inner diameter of the lower electrode 220 , b represents the distance between the lower electrodes 220 , c represents the vertical height of the outer surface of the lower electrode 220 , and min(a, b) represents the smaller number of a and b.

[0158] The aspect ratio AR of the lower electrode 220 may be, for example, 30 or more, or 45 or more. For example, the aspect ratio AR of the lower electrode 220 may range from about 30 to about 200, about 40 to about 150, about 45 to about 120, about 50 to about 100, or about 55 to about 80.

[0159] In addition, a ratio of the minimum thickness of the capacitor dielectric film 222 formed on the surface of the lower electrode 220 to the maximum thickness of the capacitor dielectric film 222 may be approximately 0.85 or higher, approximately 0.9 or higher, approximately 0.93 or higher, approximately 0.95 or higher, approximately 0.96 or higher, approximately 0.97 or higher, approximately 0.98 or higher, or approximately 0.99 or higher.

[0160] Figures 10A-10C 4 is a diagram illustrating a method of manufacturing a semiconductor device 400 according to example embodiments. Figure 10A FIG. 4 is a top view of a semiconductor device 400 to be formed. Figure 10B for Figure 10A 4 is a perspective view of a semiconductor device 400. Figure 10C To follow Figure 10A A cross-sectional view of the cross-sectional structure taken along lines XX' and YY'.

[0161] Reference Figures 10A-10CThe semiconductor device 400 can include a fin-shaped active region FA, which can protrude from the substrate 402.

[0162] Since the substrate 402 is substantially the same as the substrate 210 described above, a detailed description thereof is omitted here. Figure 6A

[0163] The substrate 402 can include a III-V material or a Group IV material, which can be used as a material for a channel of a high-power high-speed transistor. When an NMOS transistor is formed on the substrate 402, the substrate 402 can include any of III-V materials. For example, the substrate 402 can include GaAs. When a PMOS transistor is formed on the substrate 402, the substrate 402 can include a semiconductor material (e.g., germanium) having a higher hole mobility than a silicon substrate.

[0164] The fin-shaped active region FA can extend in one direction (e.g., a Y direction in FIG. 4) on the substrate 402. The fin-shaped active region FA can be formed by etching the substrate 402 in the Y direction. Figure 10A and 10B A device isolation layer 410 can be formed on the substrate 402 to cover a lower sidewall of the fin-shaped active region FA. The fin-shaped active region FA can protrude as a fin on the device isolation layer 410. In some example embodiments, the device isolation layer 410 can be a dielectric, and can include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a combination thereof, but the inventive concept is not limited thereto.

[0165] A gate structure 420 can be formed on the substrate 402 and extend over the fin-shaped active region FA in a direction (e.g., an X direction) crossing the extension direction of the fin-shaped active region FA. A pair of source and drain regions 430 can be formed in the fin-shaped active region FA on both sides of the gate structure 420.

[0166] The pair of source and drain regions 430 can include a semiconductor layer epitaxially grown from the fin-shaped active region FA. Each of the pair of source and drain regions 430 can have (i) an embedded silicon germanium (SiGe) structure including a plurality of epitaxially grown silicon germanium layers, (ii) an epitaxially grown silicon layer, or (iii) an epitaxially grown silicon carbide (SiC) layer. Figure 10B A case in which the pair of source and drain regions 430 has a specific shape is described, but the cross-sectional shape of each of the pair of source and drain regions 430 is not limited to the cross-sectional shape shown in FIG. 4B and has various shapes. For example, the pair of source and drain regions 430 can have various cross-sectional shapes such as a circular cross-sectional shape, an elliptical cross-sectional shape, or a polygonal cross-sectional shape. Figure 10B

[0167] ​​A MOS transistor TR can be formed at the intersection between the fin-shaped active region FA and the gate structure 420. The MOS transistor TR can include a three- dimensional (3D) MOS transistor having a channel formed on the top surface and two side surfaces of the fin-shaped active region FA. The MOS transistor TR can constitute an NMOS transistor or a PMOS transistor.

[0168] As shown in FIG. 4A, the gate structure 420 can include an interface layer 412, a high-k dielectric film 414, a first metal-containing layer 426A, a second metal-containing layer 426B, and a gap fill metal layer 428, which can be sequentially formed on the surface of the fin-shaped active region FA. Among the gate structure 420, the first metal-containing layer 426A, the second metal-containing layer 426B, and the gap fill metal layer 428 can constitute the gate electrode 420G. Figure 10C An insulating spacer 442 can be formed on the two side surfaces of the gate structure 420. An interlayer insulating layer 444 can be formed to cover the insulating spacer 442 opposite (oppositely) to the gate structure 420 across the insulating spacer 442.

[0169] The interface layer 412 can be formed on the surface of the fin-shaped active region FA. The interface layer 412 can include an insulating material such as an oxide film, a nitride film, or an oxynitride film. The interface layer 412 can constitute a gate insulating film together with the high-k dielectric film 414.

[0170] The high-k dielectric film 414 can include a material having a higher dielectric constant than a silicon oxide film. In some example embodiments, the high-k dielectric film 414 can include at least two of silicon (Si), strontium (Sr), barium (Ba), titanium (Ti), lead (Pb), zirconium (Zr), and hafnium (Hf). For example, the high-k dielectric film 414 can have a dielectric constant of about 4 to about 100. The high-k dielectric film 414 can include a combination of oxidized metals and / or semimetals such as zirconium oxide, zirconium silicon oxide, hafnium oxide, hafnium oxynitride, hafnium silicon oxide, tantalum oxide, titanium oxide, barium strontium titanium oxide, barium titanium oxide, strontium titanium oxide, yttrium oxide, aluminum oxide, lead scandium tantalum oxide, lead zinc niobate, and combinations thereof, but the material forming the high-k dielectric film 414 is not limited thereto.

[0171] The high-k dielectric film 414 can be formed by using an atomic layer deposition (ALD) process. The high-k dielectric film 414 can be formed by a method of forming an oxide film as described with reference to

[0172] Figures 1-3D FIGS. 5A to 5F, but the method of forming the high-k dielectric film 414 is not limited thereto.

[0173] ​In some example embodiments, the first metal-containing layer 426A can include titanium nitride, tantalum nitride, titanium oxynitride, or tantalum oxynitride. For example, the first metal-containing layer 426A can include TiN, TaN, TiAlN, TaAlN, TiSiN, or a combination thereof. The first metal-containing layer 426A can be formed by using a variety of deposition methods, such as an ALD process, a chemical vapor deposition (CVD) process, or a physical vapor deposition (PVD) process.

[0174] The first metal-containing layer 426A can include a single layer or a multi-layer structure.

[0175] In some example embodiments, the second metal-containing layer 426B can include an N-type metal-containing layer that is required for an NMOS transistor including a titanium or tantalum containing aluminum compound. For example, the second metal-containing layer 426B can include titanium aluminum carbide (TiAlC), titanium aluminum nitride (TiAlN), titanium aluminum carbonitride (TiAlCN), titanium aluminum (TiAl), tantalum aluminum carbide (TaAlC), tantalum aluminum nitride (TaAlN), tantalum aluminum carbonitride (TaAlCN), tantalum aluminum (TaAl), or a combination thereof.

[0176] In some further example embodiments, the second metal-containing layer 426B can include a p-type metal-containing layer that is required for a PMOS transistor. For example, the second metal-containing layer 426B can include at least one of molybdenum (Mo), palladium (Pd), ruthenium (Ru), platinum (Pt), titanium nitride (TiN), tungsten nitride (WN), tantalum nitride (TaN), iridium (Ir), tantalum carbide (TaC), ruthenium nitride (RuN), and molybdenum nitride (MoN).

[0177] The second metal-containing layer 426B can include a single layer or a multi-layer structure.

[0178] The second metal-containing layer 426B can be used to control the work function of the gate structure 420 together with the first metal-containing layer 426A. The threshold voltage of the gate structure 420 can be controlled by adjusting the work functions of the first metal-containing layer 426A and the second metal-containing layer 426B. In some example embodiments, either one of the first metal-containing layer 426A and the second metal-containing layer 426B can be omitted.

[0179] When the gate structure 420 is formed by a replacement metal gate (RMG) process, the gap fill metal layer 428 can be formed to fill the remaining gate space on the second metal-containing layer 426B. When there is no remaining gate space on the second metal-containing layer 426B after the second metal-containing layer 426B is formed, the gap fill metal layer 428 can not be formed on the second metal-containing layer 426B but be omitted.

[0180] The gap fill metal layer 428 can include a material selected from the group consisting essentially of tungsten (W), metal nitrides (e.g., TiN and TaN), aluminum (Al), metal carbides, metal silicides, metal aluminum carbides, metal aluminum nitrides, and metal silicon nitrides.

[0181] In a method of manufacturing the semiconductor device 400 as described with reference to Figures 10A-10C , the high-k dielectric film 414 can be formed by using the method of forming an oxide film according to an example embodiment. That is, the formation of the high-k dielectric film 414 can include forming an adsorption layer of a combination of a first source material and an electron donor compound on the fin-type active region FA in which the interface layer 412 is formed, forming an adsorption layer of a second source material, and supplying an oxidizing agent to form an oxide film containing at least two central atoms.

[0182] A method of manufacturing the semiconductor device 400 including a FinFET including a 3D channel has been described with reference to Figures 10A-10C , but the inventive concept is not limited thereto. For example, it will be apparent to those of ordinary skill in the art that a method of manufacturing a semiconductor device including a planar MOSFET having characteristics according to an example embodiment can be provided by making various changes in form and details to the example embodiments described above within the spirit and scope of the inventive concept.

[0183] Figure 11 A cross-sectional view of another example of a semiconductor device formed by a method of manufacturing the semiconductor device 500 according to an example embodiment.

[0184] With reference to Figure 11 , the interlayer insulating films 510 can be vertically stacked on the semiconductor substrate 501. The conductive patterns 570 can be interposed between the interlayer insulating films 510.

[0185] The vertical structures 540 can pass through the conductive patterns 570 and the interlayer insulating films 510. The vertical structures 540 can each include a core pattern 525, a pad pattern 530, and an outer pattern 520 surrounding side surfaces of the core pattern 525 and extending on side surfaces of the pad pattern 530.

[0186] The core pattern 525 can include an insulating material such as silicon oxide.

[0187] The pad pattern 530 can be located on the core pattern 525 at a higher level than the uppermost conductive pattern of the conductive patterns 570. The pad pattern 530 can include a conductive material such as doped polysilicon.

[0188] The outer pattern 520 can include a semiconductor pattern which can be used as a channel of a transistor. For example, the outer pattern 520 can include a semiconductor material such as silicon. A portion of the outer pattern 520 near the conductive pattern 570 can include a dielectric material. The dielectric material can include a material which can be used as a tunnel oxide film of a transistor (e.g., silicon oxide). The dielectric material can include a material which can store information of a flash memory device (e.g., silicon nitride or a high-k dielectric material). The dielectric material can be formed by the method of forming an oxide film according to an example embodiment.

[0189] Meanwhile, the conductive pattern 570 can include a metal nitride film and / or a metal film. For example, the conductive pattern 570 can each include a metal film and a metal nitride film interposed between the metal film and the interlayer insulating film 510. Further, the metal nitride film can extend between the metal film and the vertical structure 540. The conductive pattern 570 can be formed by the method of forming a material film according to an example embodiment.

[0190] The cap insulating film 550 can be provided to cover the interlayer insulating film 510 and the vertical structure 540.

[0191] While the present inventive concept has been particularly shown and described with reference to example embodiments thereof, it will be understood that various changes in form and details can be made therein without departing from the spirit and scope of the appended claims.

Claims

1. A method for forming an oxide film including at least two non-oxygen elements, the method comprising: providing a first source material on a substrate, the first source material comprising a first central element; providing an electron donor compound to combine with the first source material; providing a second source material on the substrate after providing the electron donor compound, the second source material including a second central element; and providing an oxidizing agent on the substrate, The first central element in the first source material and the second central element in the second source material are different from each other and are each independently a metal or a semi-metal.

2. The method of claim 1, wherein The electron donor compound includes an oxygen-containing, nitrogen-containing, sulfur-containing, or phosphorus-containing hydrocarbon compound having an unshared electron pair.

3. The method of claim 1, wherein The electron donor compound includes at least one of the following: a C1-C10 alcohol compound, a C2-C10 ether compound, a C3-C10 ketone compound, a C6-C12 aromatic compound, a C3-C15 allyl compound, a C4-C15 diene compound, a C5-C20 β-diketone compound, a C5-C20 β-ketimine compound, a C5-C20 β-diimine compound, ammonia, a C1-C10 amine compound, a C1-C10 thiol compound, and a C2-C10 sulfide compound.

4. The method of claim 1, further comprising The electron donor compound is provided on the substrate before providing the first source material on the substrate.

5. The method of claim 4, further comprising The electron donor compound is provided on the substrate after providing the second source material on the substrate and before providing the oxidant.

6. The method of claim 1, further comprising The electron donor compound is provided on the substrate after providing the second source material on the substrate and before providing the oxidant.

7. The method of claim 1, wherein Providing the first source material on the substrate at least partially overlaps in time with providing the electron donor compound.

8. The method of claim 1, wherein The first central element and the second central element each independently include at least one of the following: beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), rubidium (Rb), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (S n), antimony (Sb), tellurium (Te), cesium (Cs), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), polonium (Po), francium (Fr), radium (Ra), actinium (Ac), thorium (Th), protactinium (Pa), and uranium (U).

9. The method of claim 1, wherein The oxidant includes at least one of H2O, O2, O3, N2O, NO, NO2, N2O4, H2O2, C1-C10 alcohols, C2-C10 ethers, C3-C10 ketones, C1-C10 carboxylic acids, and C1-C10 esters.

10. The method of claim 1, wherein An atomic layer deposition cycle includes providing the first source material on the substrate, providing the electron donor compound, providing the second source material on the substrate, and providing the oxidant, The atomic layer deposition cycle is performed multiple times.

11. A method for manufacturing a semiconductor device, the method comprising: forming a lower electrode electrically connected to the active region of the semiconductor substrate; forming a dielectric film on the exposed surface of the lower electrode; and forming an upper electrode on the dielectric film, wherein forming a dielectric film comprises: providing a first source material on the exposed surface of the lower electrode; providing an electron donor compound capable of forming a van der Waals bond with the first source material; providing a second source material on the lower electrode after providing the electron donor compound; and providing an oxidant on the lower electrode, wherein the first source material comprises a first central element that is a metal or a semi-metal, The second source material includes a second central element that is a metal or a semi-metal, and The first central element in the first source material and the second central element in the second source material are different from each other.

12. The method of claim 11, wherein The electron donor compound includes an oxygen-containing, nitrogen-containing, sulfur-containing, or phosphorus-containing hydrocarbon compound having an unshared electron pair.

13. The method of claim 12, wherein The electron donor compound includes at least one of the following: a C1-C10 alcohol compound, a C2-C10 ether compound, a C3-C10 ketone compound, a C6-C12 aromatic compound, a C3-C15 allyl compound, a C4-C15 diene compound, a C5-C20 β-diketone compound, a C5-C20 β-ketimine compound, a C5-C20 β-diimine compound, ammonia, a C1-C10 amine compound, a C1-C10 thiol compound, and a C2-C10 sulfide compound.

14. The method of claim 12, wherein The electron donor compound includes a C1-C10 alcohol compound, a C2-C10 ether compound, a C3-C10 ketone compound, or a C1-C10 amine compound.

15. The method of claim 11, wherein The first central element and the second central element are each boron (B), aluminum (Al), silicon (Si), germanium (Ge), scandium (Sc), yttrium (Y), lanthanum (La), titanium (Ti), zirconium (Zr), or hafnium (Hf).

16. The method of claim 12, wherein The time point when supply of the electron donor compound starts is earlier than the time point when supply of the first source material starts.

17. The method of claim 16, wherein The time point when supply of the electron donor compound ends is later than the time point when supply of the first source material ends.

18. The method of claim 12, wherein Providing the first source material on the exposed surface of the lower electrode at least partially overlaps in time with providing the electron donor compound.

19. A method of forming a dielectric film, the method comprising: providing a substrate into the reaction chamber; providing a first electron donor compound on the substrate; and Repeating the deposition cycle until an oxide film is formed on the substrate to a set thickness, The deposition cycle comprises: providing a first source material on the substrate, the first source material comprising a first central element; providing a second electron donor compound to combine with the first source material; providing a second source material on the substrate after providing the second electron donor compound, the second source material including a second central element; and providing an oxidizing agent on the substrate, The first central element in the first source material and the second central element in the second source material are different from each other and are each independently a metal or a semi-metal.

20. The method of claim 19, wherein providing the first source material on the substrate and providing the second source material on the substrate are performed separately in time, and Providing the second electron donor compound is performed at least partially in time between providing the first source material on the substrate and providing the second source material on the substrate.

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