Film-forming materials, film-forming compositions, film-forming methods using the same, and semiconductor devices produced thereby

Abstract

The present invention relates to a film forming material, a film forming composition, a film forming method using the same, and a semiconductor device manufactured thereby, according to which a growth rate is reduced, thereby providing a conformal thin film even when a thin film is formed on a substrate having a complex structure, and an effect of reducing impurities in the thin film and greatly increasing the density of the thin film to greatly reduce a leakage current due to oxidation of a lower electrode in a conventional high-temperature process is provided.

Description

Technical Field

[0001] This invention relates to a film-forming material, a film-forming composition, a film-forming method using the same, and a semiconductor device thus prepared. Specifically, it relates to inducing ligand exchange with unwanted components on a substrate while controlling the film formation rate through the film-forming material contained in the film-forming composition, thereby producing a high-purity conformal and denser film in a bottom-up manner, improving the film quality formed by chemical reaction with the substrate to improve crystallinity, reducing the impurity concentration in the film to reduce leakage current, and a film-forming method using the film-forming material and a semiconductor substrate thus prepared. Background Technology

[0002] Recently, in the field of semiconductor technology, there has been active research into appropriate materials and process technologies in pursuit of higher levels of technology through the miniaturization of semiconductor devices. In particular, there is extensive research on the fabrication processes of oxide thin films such as TiO2, ZrO2, HfO2, and Al2O3, which are high-k materials used in capacitors for Dynamic Random Access Memory (DRAM) in semiconductor processes.

[0003] In semiconductor manufacturing, metal-organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) are commonly used as processes for forming metal oxide thin films. However, several limitations have emerged when forming metal oxide thin films using MOCVD and ALD. First, the oxidation of the lower electrode caused by miniaturization of semiconductor devices and high-temperature processes can lead to leakage current. Furthermore, the crystallinity of the film is low at certain temperatures, thus limiting the capacitance.

[0004] Capacitors used in DRAM require high capacitance and 10 -7 A / cm 2 The following leakage current, in particular, is a major variable for meeting the stringent requirements of continuously decreasing DRAM cells and for providing thin-film dielectric films (W. Jeon, Journal of Materials Research 35(7), 1(2019) and J. Lee, D. Park, S. Yew, S. Shin, J. Noh, H. Kim, B. Choi, IEEE Electron Device Letters 38(11)(2017)).

[0005] Niinisto et al. reported a leakage current intensity of 1 × 10⁻¹⁰ at 1 V when post-annealing 8.6 nm thick amorphous and monoclinic films formed by ALD with CpHf(NMe₂)₃ and ozone at 250–400 °C using HfO₂. -7 A / cm 2 (J. Niinisto, M. Mantymaki, K. Kukli, L. Costelle, E. Puukilainen, M. Ritala, M. Leskela, Journal of Crystal Growth, 312, 245 (2010)).

[0006] However, it is understood that in ZrO2 and HfO2, bulk-related leakage conduction mechanisms such as trap-assisted tunneling (TAT) or Poole-Frenkel emission (PF) are dominant, rather than surface-related leakage current conduction (WYChoi, G.Yoon, WYChung, Y.Cho, S.SHin and KHAhn, Micromachines 10, 256 (2019)). In particular, the carrier conduction mechanism is largely influenced by the bulk characteristics of dielectric film defects such as crystal system, internal impurities (oxygen deficiency, etc.), and external impurities that invade the film during the deposition process.

[0007] Therefore, techniques to reduce the sources of such defects in bulk ZrO2 and HfO2 are more effective than those using other dielectric materials with high dielectric properties or metal electrodes with other work functions.

[0008] The thin film of the present invention aims to induce ligand exchange with unwanted components on the substrate by providing a film-forming material that simultaneously provides a capping agent and a ligand exchange reactant, and to reduce leakage current while improving film quality and film conformality, and to ensure the reliability of semiconductor devices at a low temperature of 250°C. Summary of the Invention

[0009] Technical issues

[0010] The purpose of this invention is to reduce impurities in the film and significantly increase the film density to reduce leakage current, even when forming a thin film on a substrate with a complex structure, while reducing the growth rate to provide a conformal film.

[0011] In addition, the purpose of this invention is to provide a film with a high dielectric constant (high-k) at low temperatures, thereby ensuring the reliability of semiconductor devices.

[0012] Technical solution

[0013] To achieve the above objectives, the present invention provides a film-forming material comprising a capping agent and a ligand exchange reactant.

[0014] The capping agent can be an unsaturated hydrocarbon with 2 to 15 carbon atoms formed from the film-forming material during the film-forming process.

[0015] The ligand exchange reactant can be hydrogen halide or halogen gas formed by the film-forming material during the film-forming process and reacting with the ligands of the inorganic precursor.

[0016] The film-forming material can be a branched compound, cyclic compound, or aromatic compound represented by chemical formula 1.

[0017] Chemical Formula 1:

[0018] A n B m X o Y i Z j

[0019] Wherein, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3.

[0020] In addition, the present invention provides a bottom-up thin film composition comprising a pulse precursor.

[0021] The pulse precursor may be a mixed precursor comprising the above-mentioned film-forming material (hereinafter also referred to as "organic precursor") and an inorganic precursor.

[0022] The inorganic precursor may contain one or more of the following: Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn.

[0023] The inorganic precursor may be one or more film residual precursors selected from compounds represented by chemical formula 2a, compounds represented by chemical formula 2b, and compounds represented by chemical formula 2c.

[0024] Chemical formula 2a:

[0025]

[0026] Wherein, M1 is Zr, Hf, Si, Ge or Ti, X1, X2, X3 are independently -NR1R2 or -OR3, R1 to R3 are independently alkyl groups having 1 to 6 carbon atoms, and n is 1 or 2.

[0027] Chemical formula 2b:

[0028]

[0029] Wherein, M2 is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer from 0 to 5, X′1, X′2 and X′3 are independently -NR′1R′2 or -OR′3, and R′1 to R′3 are independently alkyl groups having 1 to 6 carbon atoms.

[0030] Chemical formula 2c:

[0031]

[0032] Wherein, the M 1 Zr, Hf, Si, Ge or Ti, X 11 and X 12 Each is independently alkyl or selected from -NR 3 R 4 and -OR 5 Any of the following, the R 1 ~R 5 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein n 1 and n2 Each is an integer from 0 to 5, independent of the others.

[0033] The weight ratio of the inorganic precursor to the film-forming material can be 1:99 to 99:1.

[0034] The composition may contain a reactive gas.

[0035] The reactant gas can be an oxidizing agent, a nitriding agent, or a reducing agent.

[0036] The film-forming composition can be used for bottom-up film formation or selective regional film formation.

[0037] In addition, the present invention provides a film-forming method, which includes the following steps:

[0038] The aforementioned film-forming material is injected into the cavity and deposited onto the loaded substrate;

[0039] Inorganic precursors are implanted onto the substrate and deposited; and

[0040] A reactive gas is injected onto the substrate and deposited thereon, wherein the inorganic precursor comprises one or more substances selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn.

[0041] In addition, the present invention provides a film-forming method, which includes the following steps:

[0042] Inorganic precursors are injected into the chamber and deposited onto the loaded substrate;

[0043] Implanting the aforementioned film-forming material onto the substrate and depositing it; and

[0044] Reactive gases are injected onto the substrate and deposition is performed.

[0045] The inorganic precursor comprises one or more substances selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn.

[0046] In addition, the present invention provides a film-forming method, which includes the following steps:

[0047] The aforementioned film-forming material and inorganic precursor are injected into the chamber and deposited onto the loaded substrate; and

[0048] Reactive gases are injected onto the substrate and deposition is performed.

[0049] The inorganic precursor comprises one or more substances selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn.

[0050] The film-forming method may include the following steps: depositing an end-capping agent and a ligand exchange reactant formed from the film-forming material onto a substrate; and the ligand exchange reactant performing an exchange reaction on the ligands of the inorganic precursor.

[0051] The inorganic precursor may remain on the substrate, while the film-forming material may not remain on the substrate.

[0052] The aspect ratio of the substrate can be 10:1 or higher.

[0053] The film-forming material and the inorganic precursor can be provided in a pulsed manner.

[0054] The film-forming method can be carried out at temperatures ranging from 200°C to 800°C.

[0055] The reactant gas may be an oxidizing agent, a reducing agent, or a nitriding agent.

[0056] The film formation method can be implemented by atomic layer deposition, chemical vapor deposition, plasma atomic layer deposition, or plasma chemical vapor deposition.

[0057] The film formation method can be bottom-up film formation.

[0058] The film formation method can use metal oxide films, metal nitride films, metal films, or two or more of them to form films with selective regions.

[0059] In addition, the present invention provides a bottom-up thin film formation method, which includes the following steps: injecting a bottom-up thin film composition comprising a pulse precursor into a chamber, and depositing the inorganic precursor from bottom to top onto the surface of a substrate loaded in the chamber, wherein the pulse precursor comprises the aforementioned film-forming material and the precursor.

[0060] The step of depositing the inorganic precursor onto the substrate from bottom to top may include the following steps: injecting the film-forming material onto the substrate and purging it; and injecting a reactive gas onto the substrate and purging it.

[0061] The step of depositing the inorganic precursor onto the substrate from bottom to top may include the following steps: injecting the inorganic precursor onto the substrate and purging it; injecting the film-forming material onto the substrate and purging it; and injecting a reactive gas onto the substrate and purging it.

[0062] The step of depositing the inorganic precursor onto the substrate from bottom to top may include the following steps: injecting the film-forming material onto the substrate and purging it; injecting a reactive gas onto the substrate and purging it; and injecting the film-forming material onto the substrate and purging it.

[0063] The step of depositing the inorganic precursor onto the substrate from bottom to top may include the following steps: simultaneously injecting the inorganic precursor and the organic precursor onto the substrate and purging; and injecting a reactive gas onto the substrate and purging.

[0064] The aspect ratio of the substrate can be 10:1 or higher.

[0065] The film-forming material and the inorganic precursor can be provided in a pulsed manner.

[0066] The film-forming method can be carried out at temperatures ranging from 200°C to 800°C.

[0067] The reactant gas may be an oxidizing agent, a reducing agent, or a nitriding agent.

[0068] The inorganic precursor may remain on the substrate, while the film-forming material may not remain on the substrate.

[0069] The bottom-up thin film formation method can be implemented by atomic layer deposition, chemical vapor deposition, plasma atomic layer deposition, or plasma chemical vapor deposition.

[0070] The bottom-up thin film formation method can use metal oxide thin films, metal nitride thin films, metal thin films, non-metal oxide thin films, non-metal nitride thin films, other dielectric thin films, or two or more of them to form thin films with selective regions. Here, non-metal refers to materials other than metals known in the art; for example, it could be silicon.

[0071] In addition, the present invention provides a semiconductor substrate manufactured by the above-described film formation method.

[0072] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal capacitors, DRAM trench capacitors, 3D gate-all-around (GAA) capacitors, or 3D NAND.

[0073] In addition, the present invention provides a semiconductor device comprising the above-described semiconductor substrate.

[0074] Beneficial effects

[0075] According to the present invention, a film-forming material is provided that simultaneously provides a capping agent and a ligand exchange reactant during the film-forming process.

[0076] According to the present invention, a film-forming composition is provided that induces ligand exchange with components that are not desired to remain on the substrate through the film-forming material, and can provide a conformal film even when forming a film on a substrate with a complex structure.

[0077] According to the present invention, a film-forming composition has the effect of providing more effective removal of process byproducts and unwanted residual components generated during film formation, and reducing the deposition rate to appropriately reduce the film formation rate and improve the crystallinity of the film, thereby improving the quality of the film.

[0078] According to the present invention, it has the effect of providing a bottom-up thin film composition, which can provide a conformal thin film in a bottom-up manner even when a thin film is formed on a substrate with a complex structure.

[0079] According to the present invention, a film composition is provided that more effectively removes process byproducts during the formation of bottom-up films, reduces the deposition rate to appropriately reduce the film growth rate, and improves the crystallinity of the film, thereby improving the quality of the film.

[0080] According to the present invention, film-forming compositions are provided that can reduce impurities in the thin film and significantly increase the density of the thin film to reduce leakage current caused by oxidation of the lower electrode in existing high-temperature processes, thereby providing the effects of film-forming methods using them and semiconductor devices manufactured therefrom. Attached Figure Description

[0081] Figure 1 The diagrams schematically illustrate the film-forming cycle of the film-forming composition of the present invention. The left diagram shows the film-forming cycle in which the inorganic precursor is added after the film-forming material is added (hereinafter referred to as the "first step"), and the right diagram shows the film-forming cycle in which the film-forming material is added after the inorganic precursor is added (hereinafter referred to as the "second step").

[0082] Figure 2 This is a GPC analysis graph showing the deposition rate of the bottom-up thin films of Examples 1 to 3, Examples 6 to 8 of the present invention, and the bottom-up thin films of Comparative Examples 1 to 6 (control group HfO2).

[0083] Figure 3 These are TEM images of cross-sections taken at 200 nm from the top and 100 nm from the bottom of HfO2 thin films deposited according to Embodiment 1 and Comparative Example 1 of the present invention on a substrate having a channel structure with an aspect ratio (length / diameter) of 22.6:1, at 320°C.

[0084] Figure 4 This is a flowchart that briefly describes the first step of Embodiment 1 of the present invention, in which the capping agent and ligand exchange reactant generated by the film-forming material during the film-forming process are deposited on the substrate and then adsorb inorganic precursors.

[0085] Figure 5 In the context of Figure 4 The flowchart briefly describes the process in which, after the capping agent and ligand exchange reactant are deposited on the substrate, inorganic precursors are adsorbed into the product, and dialkylamine and Cp, which are ligands of inorganic precursors, are exchanged by the ligand exchange reactant and a metal oxide film is generated by reacting gas.

[0086] Figure 6 The image shows a SIMS analysis graph illustrating the reduction rate of carbon (C), iodine (I), and other elements at different depths for bottom-up films manufactured at deposition temperatures of 320°C (Fig. a, Example 1 and Comparative Example 1), 300°C (Fig. b, Example 2 and Comparative Example 2), and 250°C (Fig. c, Example 3 and Comparative Example 3).

[0087] Figure 7 This is a bottom-up film density analysis diagram of the thin films manufactured at deposition temperatures of 320°C, 300°C, and 250°C for Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention.

[0088] Figure 8 This is an XPS analysis graph confirming the component content (atomic %) of bottom-up films manufactured at a deposition temperature of 250°C for different film depths in Examples 3 and Comparative Examples 3 of the present invention.

[0089] Figure 9 These are XRD pattern analysis images of the thin films manufactured at a deposition temperature of 250°C in Examples 3, 1, and 3 of the present invention. Detailed Implementation

[0090] The following provides a detailed description of the film-forming compositions, bottom-up thin film compositions, film-forming methods using them, semiconductor substrates and semiconductor devices manufactured thereby.

[0091] Unless otherwise defined, the term "capping agent" as used in this invention refers to an additive that adsorbs onto the substrate in a manner that competes with the inorganic precursor to control the film formation rate or prevent the dense adsorption of the inorganic precursor. Specific examples may be found in... Figure 4 Please confirm in (b) of the document. Figure 4 This is a flowchart that provides a brief overview of the first step in the deposition of end-capping agents and ligand exchange reactants generated during the film-forming process onto a substrate, followed by the adsorption of inorganic precursors. For example... Figure 4 As shown in (b), the film-forming material injected onto the substrate in (a) is divided into a capping agent and a ligand exchange reactant, which are weakly adsorbed onto the substrate, thereby reducing the adsorption sites of the inorganic precursor provided in (c) thereafter.

[0092] Unless otherwise defined, the term "ligand exchange reactant" as used in this invention refers to an additive that undergoes an exchange reaction with the ligands of an inorganic precursor. Specific examples may be found in... Figure 5 (a) and Figure 5 Please confirm in (b) of the document. Figure 5 In the context of Figure 4The flowchart briefly describes the process in which, after the capping agent and ligand exchange reactant are deposited on the substrate, inorganic precursors are adsorbed into the product, and dialkylamine and Cp, which are ligands of inorganic precursors, are exchanged by the ligand exchange reactant and a metal oxide film is generated by reacting gas.

[0093] like Figure 5 As shown, the product of the first step (equivalent to) adsorbing inorganic precursors after the above-mentioned end-capping agent and ligand exchange reactant are deposited on the substrate. Figure 4 (d) or Figure 5 In (a) of the above, an exchange reaction occurs with a dialkylamine, which is a ligand for an inorganic precursor (equivalent to...). Figure 5 (a) in the middle) and the exchange reaction with Cp, another ligand as an inorganic precursor (equivalent to Figure 5 (b) of the mixture contains halogens that remain at that location, which then react with the injected reactive gas to form a metal oxide film.

[0094] Unless otherwise defined, the term "bottom-up" as used in this invention refers to growth starting from the bottom on a substrate with a channel structure, wherein, as an example, a substrate with a channel structure may refer to an aspect ratio of 10:1 or more or 20:1 or more.

[0095] Unless otherwise defined, the aspect ratio refers to the ratio of the length to the diameter (L / D) of the channel structure, where length and diameter are defined as commonly referred to in this art.

[0096] The inventors of this invention have confirmed that when a film-forming composition comprising an inorganic precursor and a film-forming material is used to form a film on the surface of a substrate loaded inside a chamber, even at temperatures as low as 250°C, the growth rate of the upper and lower portions of the film formed after deposition can be significantly reduced, ultimately resulting in a substantial improvement in the conformal characteristics of channel structures with high aspect ratios. Furthermore, unexpectedly, a reduction in the residual amounts of carbon and iodine, along with a significant improvement in film density and impurities, were confirmed. Based on this, further research was conducted, leading to the completion of this invention.

[0097] As one embodiment, the film formation method may include the following steps: vaporizing the inorganic precursor and the film-forming material separately or simultaneously and adsorbing them onto the surface of a substrate loaded in a chamber; purging the interior of the chamber with a purge gas; supplying a reaction gas into the interior of the chamber; and purging the interior of the chamber with a purge gas. In this case, the advantage is that the film formation rate is appropriately reduced, and even if the deposition temperature is reduced during film formation, the density, crystallinity, conformal properties, and dielectric properties of the film can be improved, and the leakage current is effectively reduced, thereby significantly improving the film quality.

[0098] In a preferred embodiment, the film formation method may include the following steps: injecting a bottom-up thin film composition containing a pulse precursor into a chamber and depositing it on the surface of a loaded substrate, wherein the pulse precursor contains an inorganic precursor and an organic precursor, and after simultaneously injecting the inorganic precursor and the organic precursor onto the substrate, injecting a reactive gas and performing deposition. In this case, the advantage is that the film growth rate is appropriately reduced, and even if the deposition temperature is reduced during film formation, the density, crystallinity, conformal properties, and dielectric properties of the bottom-up film can be improved, and the leakage current can be effectively reduced, thereby significantly improving the film quality.

[0099] In another preferred embodiment, the film formation method may include the following steps: injecting a film-forming material into a chamber and depositing it onto a loaded substrate; injecting an inorganic precursor onto the substrate and depositing it; and injecting a reactive gas onto the substrate and depositing it. In this case, the advantage is that the film formation rate is appropriately reduced, and even if the deposition temperature is reduced during film formation, the density, crystallinity, conformal properties, and dielectric properties of the film can be improved, and the leakage current can be effectively reduced, thereby significantly improving the film quality.

[0100] As another preferred embodiment, the film formation method may include the following steps: injecting an inorganic precursor into a chamber and depositing it onto a loaded substrate; injecting a film-forming material onto the substrate and depositing it; and injecting a reactive gas onto the substrate and depositing it. In this case, the advantage is that the film formation rate is appropriately reduced, and even if the deposition temperature is reduced during film formation, the density, crystallinity, conformal properties, and dielectric properties of the film can be improved, and the leakage current is effectively reduced, thereby significantly improving the film quality.

[0101] In another preferred embodiment, the film formation method may include the following steps: injecting film-forming material and inorganic precursor into a chamber and depositing them on the surface of a loaded substrate; and injecting a reactive gas onto the substrate and performing deposition. In this case, the advantage is that the film formation rate is appropriately reduced, and even if the deposition temperature is reduced during film formation, the density, crystallinity, conformal properties, and dielectric properties of the film can be improved, and the leakage current is effectively reduced, thereby significantly improving the film quality.

[0102] In another preferred embodiment, the film formation method may include the following steps: injecting a film-forming material onto a substrate and purging it; injecting an inorganic precursor onto the substrate and purging it; injecting a reactive gas onto the substrate and purging it to deposit the inorganic precursor; and injecting the film-forming material onto the substrate and purging it. In this case, the advantage is that the film formation rate is appropriately reduced, and even if the deposition temperature is reduced during film formation, the density, crystallinity, conformal properties, and dielectric properties of the film can be improved, and the leakage current can be effectively reduced, thereby significantly improving the film quality.

[0103] The thin film produced by the film-forming method can be a bottom-up thin film, in which the inorganic precursor remains and is deposited to form the thin film, but the film-forming material does not remain.

[0104] Preferably, the inorganic precursor, film-forming material, reactive gas, and purging gas can be independently delivered into the chamber via VFC, DLI, or LDS. More preferably, they can be delivered into the chamber via LDS.

[0105] The chamber can be a CVD chamber or an ALD chamber, but is not limited to these.

[0106] In one embodiment of the present invention, the film-forming material may include a capping agent and a ligand exchange reactant.

[0107] like Figure 4 As shown in (b), the blocking agent can be an unsaturated hydrocarbon with 2 to 15 carbon atoms formed from the film-forming material during the film-forming process. An unsaturated hydrocarbon with 2 to 15 carbon atoms having a tertiary structure can maximize the blocking effect of preventing inorganic precursors from adsorbing onto the substrate, and is therefore preferred.

[0108] like Figure 5 As shown in (a) and (b), the ligand exchange reactant can be hydrogen halide or halogen gas formed by the film-forming material in the film-forming process and exchanged with the ligands of the inorganic precursor. Hydrogen halide is preferred because it can simultaneously maximize the end-capping effect of preventing the inorganic precursor from adsorbing onto the substrate and the effect of exchanging with the ligands of the inorganic precursor adsorbed in an adjacent manner.

[0109] At this point, halogens such as F, Cl, Br, or I can be used. Considering the subsequent reactivity with the reacting gases, I or Br is preferred.

[0110] The film-forming material used in this invention refers to a material that has no substantial reactivity with the inorganic precursors described later and will not remain in the film. For example, it is a branched compound, cyclic compound or aromatic compound represented by chemical formula 1. In this case, the advantage is that, as a precursor that will not remain in the film, it can effectively achieve the objective effect of this invention and provide a high dielectric constant.

[0111] Chemical Formula 1:

[0112] A n B m X o Y i Z j

[0113] Wherein, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3.

[0114] Unless otherwise defined, the term "no residue" as used in this invention refers to the presence of less than 0.1 atomic percent (atom%) of C and less than 0.1 atomic percent (atom%) of N as determined by XPS analysis.

[0115] Preferably, the film-forming material can be a compound with a purity of 99.9% or higher, a compound with a purity of 99.95% or higher, or a compound with a purity of 99.99% or higher. For reference, when using a compound with a purity of less than 99%, impurities will be formed, so materials with a purity of 99% or higher should be used as much as possible.

[0116] As an example of the capping agent and ligand exchange agent formed from the film-forming material, when the film-forming material is tert-butyl iodine, the capping agent may be 2-methylpropene, and the ligand exchange agent may be hydrogen iodide.

[0117] The film-forming material can be supplied in a pulsed manner using a vapor flow controller (VFC) and / or a liquid delivery system (LDS), where the pulsed manner is any pulsed state used in the art.

[0118] In one embodiment of the present invention, the film-forming composition may simultaneously comprise the film-forming material and an inorganic precursor.

[0119] In one embodiment of the present invention, the film-forming composition may be a bottom-up film composition.

[0120] In one embodiment of the invention, the bottom-up thin film composition may include a pulse precursor.

[0121] In this invention, a pulse precursor refers to a precursor that can be supplied in a pulsed manner using a vapor flow controller (VFC) and / or a liquid delivery system (LDS). In this case, the pulsed state can be any pulse state commonly used in the art.

[0122] As an example, the pulse precursor may be a mixed precursor comprising inorganic and organic precursors.

[0123] The inorganic precursor used in this invention refers to a material that remains in the thin film and helps improve conductivity; for example, it can be a material represented by chemical formula 2. In this case, the advantage is that it effectively achieves the objective effect of the invention and has a high dielectric constant.

[0124] Chemical formula 2:

[0125] M x L y

[0126] Wherein, x is an integer from 1 to 3, and M can be selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy The ligands are selected from H, C, N, O, F, P, S, Cl, Br or I or H, C, N, O, F, P, S, Cl and Br, where y is an integer from 1 to 6, and L is a ligand composed of two or more combinations of H, C, N, O, F, P, S, Cl and Br, or I or H, C, N, O, F, P, S, Cl and Br, respectively.

[0127] In a preferred embodiment, the inorganic precursor is one or more film residual precursors selected from compounds represented by chemical formula 2a, chemical formula 2b, and chemical formula 2c, in which case thermal stability and reactivity are preferred.

[0128] Chemical formula 2a:

[0129]

[0130] Wherein, M1 is Zr, Hf, Si, Ge or Ti, X1, X2, X3 are independently -NR1R2 or -OR3, R1 to R3 are independently alkyl groups having 1 to 6 carbon atoms, and n is 1 or 2.

[0131] Chemical formula 2b:

[0132]

[0133] Wherein, M2 is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer from 0 to 5, X′1, X′2 and X′3 are independently -NR′1R′2 or -OR′3, and R′1 to R′3 are independently alkyl groups having 1 to 6 carbon atoms.

[0134] Chemical formula 2c:

[0135]

[0136] Wherein, M1 is Zr, Hf, Si, Ge or Ti, X 11 and X 12 Each of the R1 to R5 is independently an alkyl group or selected from -NR3R4 and -OR5, wherein each of the R1 to R5 is an alkyl group having 1 to 6 carbon atoms, and the n 1 and n 2 Each is an integer from 0 to 5, independent of the others.

[0137] The weight ratio of the inorganic precursor to the film-forming material can be 1:99 to 99:1, 1:90 to 90:1, 1:85 to 85:1, or 1:80 to 80:1.

[0138] The composition comprises a pulse of reactive gas, and the reactive gas may be one or more selected from oxidizing agents, nitriding agents, and reducing agents.

[0139] The oxidizing agent, nitriding agent, and reducing agent can be substances commonly used in this technical field. For example, the oxidizing agent can be O3, O2, or a mixture thereof, the nitriding agent can be NH3, N2H2, N2, or a mixture thereof, and the reducing agent can be H2, etc., but is not limited to these.

[0140] The film-forming method of the present invention includes the step of depositing an inorganic precursor on a substrate using a film-forming material.

[0141] As an example, in the film formation method of the present invention, the step of depositing the inorganic precursor on the substrate may include the following steps: depositing an end-capping agent and a ligand exchange reactant formed from the film-forming material on the substrate; and the ligand exchange reactant undergoing an exchange reaction with the ligands of the inorganic precursor to deposit the inorganic precursor on the substrate.

[0142] As a preferred example, in the film formation method of the present invention, the step of depositing the inorganic precursor on the substrate may include the following steps: depositing an end-capping agent and a ligand exchange reactant formed from the film-forming material on the substrate; the ligand exchange reactant undergoing an exchange reaction with the ligands of the inorganic precursor; and injecting a reactive gas onto the substrate to deposit the inorganic precursor.

[0143] At this time, the inorganic precursor can be added after the film-forming material is injected, or before the film-forming material is injected, or at the same time as the film-forming material is injected.

[0144] As a preferred example, in the bottom-up film formation method of the present invention, the step of depositing the inorganic precursor on the substrate from bottom to top may include the following steps: injecting the film-forming material onto the substrate and purging it; injecting the inorganic precursor onto the substrate and purging it; and injecting a reactive gas onto the substrate and purging it.

[0145] At this time, when the inorganic precursor is introduced after the film-forming material is injected, it can be according to the following... Figure 4 and Figure 5 The process involves end-capping and ligand exchange reactions.

[0146] As another preferred embodiment, in the bottom-up film formation method of the present invention, the step of depositing the inorganic precursor on the substrate from bottom to top may include the following steps: injecting the inorganic precursor onto the substrate and purging it; injecting the film-forming material onto the substrate and purging it; and injecting a reactive gas onto the substrate and purging it.

[0147] In another preferred embodiment, in the bottom-up film formation method of the present invention, the step of depositing the inorganic precursor on the substrate from bottom to top may include the following steps: injecting the film-forming material onto the substrate and purging it; injecting the inorganic precursor onto the substrate and purging it; injecting a reactive gas onto the substrate and purging it; and injecting the film-forming material onto the substrate and purging it.

[0148] Furthermore, as another preferred embodiment, in the bottom-up film formation method of the present invention, the step of depositing the inorganic precursor on the substrate from bottom to top may include the following steps: simultaneously injecting the inorganic precursor and the film-forming material onto the substrate and purging; and injecting a reactive gas onto the substrate and purging.

[0149] The substrate can refer to a channel structure substrate with an aspect ratio of 10:1 or higher or 20:1 or higher.

[0150] As an example, the deposition temperature of the film formation method is 200℃~800℃, specifically 200℃~600℃, preferably 250℃~450℃, specifically 250℃~420℃, 250℃~320℃, 380℃~420℃ or 400℃~450℃. Within this range, it has the advantages of significantly improving film quality and step coverage.

[0151] As an example, in the film-forming method, a reducing agent, a nitriding agent, or an oxidizing agent can be used as the reaction gas, and different reaction gases can be applied to a selected area and other areas as needed.

[0152] As an example, the film formation method can be implemented by atomic layer deposition or chemical vapor deposition, or, as needed, by plasma atomic layer deposition or plasma chemical vapor deposition.

[0153] As an example, the film formation method can use metal oxide films, metal nitride films, metal films, non-metal oxide films, non-metal nitride films, other dielectric films, or two or more of them to form films with selective regions.

[0154] According to one embodiment of the present invention, a thin film manufactured by the above-described film-forming method can be provided.

[0155] The thin film can be used as a barrier, etch stop, charge trap, selective area deposition, bottom-up film, etc.

[0156] According to one embodiment of the present invention, a semiconductor substrate manufactured by the above-described film-forming method can be provided.

[0157] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal capacitors, DRAM trench capacitors, 3D gate-all-around (GAA) capacitors, or 3D NAND.

[0158] Furthermore, according to another embodiment of the present invention, a semiconductor device comprising the above-described semiconductor substrate may be provided.

[0159] As an example, the capacitor including the thin film of the present invention can be stacked in two to three or more layers. In this case, the inorganic precursors constituting each layer can be of different types, or the same type can be used as needed.

[0160] As an example, a capacitor may be formed on the upper part of a semiconductor substrate, in which a lower electrode, a dielectric film, and a second electrode are sequentially formed.

[0161] At this point, the lower electrode can be the storage electrode of a DRAM element or other element, or the electrode of a decoupling capacitor.

[0162] As an example, the lower electrode can be manufactured in a cylindrical or columnar shape to ensure a large surface area, and can be formed of a conductive layer or a metal layer.

[0163] The dielectric film can be a metal oxide film. When the film-forming composition of the present invention is used and deposition is performed, it has the advantage that it can have a uniform thickness and appropriate viscosity even when formed on a lower electrode with a lower step or topology.

[0164] The upper electrode formed on the upper part of the dielectric film may be composed of the same conductive layer or metal layer as the lower electrode.

[0165] The following preferred embodiments and accompanying drawings are provided to aid in understanding the present invention. However, the following embodiments and accompanying drawings are merely examples of the present invention. Those skilled in the art will understand that various changes and modifications can be made within the scope and technical concept of the present invention, and these changes and modifications naturally fall within the scope of the appended claims.

[0166] [Example]

[0167] Example 1

[0168] Use shown Figure 1 The thin film manufacturing cycle shown in the left figure involves stacking HfO2 thin films from bottom to top on a SiO2 substrate with a channel structure having an aspect ratio of 22.6:1 (length:diameter).

[0169] Figure 1 The left figure corresponds to the experiment of adding an inorganic precursor after the film-forming material is added to the bottom-up thin film composition of the present invention, and is therefore referred to as the first step.

[0170] Specifically, the cycle includes the following: a 6-second purge after injecting the film-forming material for 3 seconds, a 6-second purge after injecting the inorganic precursor for 3 seconds, and a 6-second purge after injecting the reaction gas for 3 seconds.

[0171] The above-mentioned HfO2 thin film was deposited in a 12-inch ALD system equipped with a shower head.

[0172] The inorganic precursor was prepared as CpHf, a compound represented by chemical formula 3-1. CpHf was purchased from Sigma and used directly without purification.

[0173] Chemical formula 3-1:

[0174]

[0175] The film-forming material was prepared as TBI, a compound represented by chemical formula 3-2. The TBI was synthesized by the applicant and purified to a purity of 99.9% before use.

[0176] Chemical formula 3-2:

[0177]

[0178] The prepared film-forming material was loaded into a container and supplied at room temperature to a vaporizer heated to 90°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.01 g / min. The prepared CpHf was loaded into another container and supplied at a flow rate of 0.1 g / min to another vaporizer heated to 170°C.

[0179] After introducing film-forming material vaporized into a vapor phase via a vaporizer into a deposition chamber containing a substrate for 3 seconds, argon gas is supplied at 300 sccm for 6 seconds for argon purging. The substrate is formed by growing 100 nm of SiO2 on a Si wafer followed by growing a 20 nm thick TiN layer. The substrate to be formed into a metal oxide film is heated to 320°C, while the pressure within the reaction chamber is controlled at 0.74 Torr.

[0180] Next, after introducing CpHf, which has been vaporized into a vapor phase by a vaporizer, into the deposition chamber for 3 seconds, argon gas is supplied at 300 sccm for 6 seconds for argon purging. The substrate to be formed into a metal oxide film is heated to 320°C, at which point the temperature inside the reaction chamber is controlled at 0.74 Torr.

[0181] Next, after introducing ozone at 1000 sccm as a reactive gas into the reaction chamber for 3 seconds, argon gas was purged for 6 seconds. The substrate to which the metal oxide film is to be formed was heated to 320°C, at which point the temperature inside the reaction chamber was controlled at 0.74 Torr.

[0182] This process was repeated 100 times, thus forming a HfO2 thin film as a self-limiting atomic layer.

[0183] Example 2

[0184] Except that the heating temperature of the substrate was adjusted to 300°C in Example 1, the HfO2 thin film was formed in the same manner as in Example 1.

[0185] Example 3

[0186] Except that the heating temperature of the substrate was adjusted to 250°C in Example 1, the HfO2 thin film was formed in the same manner as in Example 1.

[0187] Example 4

[0188] Except that in Example 1, the inorganic precursor was replaced with tetrakis(ethylmethylamino)hafniumb (TEMAHf), a compound represented by chemical formula 3-3, an HfO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 1.

[0189] Chemical formula 3-3:

[0190]

[0191] Example 5

[0192] Except that, in Example 1, the film-forming material was replaced with TBB, a compound represented by chemical formulas 3-4, an HfO2 thin film as a self-limiting atomic layer was formed using the same method as in Example 1. The TBB was synthesized by the applicant and purified to a purity of 99.9% before use.

[0193] Chemical formula 3-4:

[0194]

[0195] Example 6

[0196] In addition to the example shown in Example 1, the method used is as follows: Figure 1 The thin film manufacturing cycle in the left figure is replaced with the one shown in the figure. Figure 1 Apart from the film manufacturing cycle shown in the right figure, the same process as in Example 1 was repeated.

[0197] Specifically, the use shown Figure 1 The film deposition cycle shown in the right figure involves stacking HfO2 thin films from bottom to top on a SiO2 substrate with a channel structure having an aspect ratio of 22.6:1 (length:diameter).

[0198] Figure 1 The right figure corresponds to the experiment of adding the film-forming material after adding the inorganic precursor of the present invention, and is therefore called the second step.

[0199] Specifically, the cycle includes the following: a 6-second purge after injecting the inorganic precursor for 3 seconds, a 6-second purge after injecting the film-forming material for 3 seconds, and a 6-second purge after injecting the reaction gas for 3 seconds. The substrate to which the metal oxide film is to be formed is heated to 320°C, and the temperature inside the reaction chamber is controlled at 0.74 Torr.

[0200] Example 7

[0201] Except that the heating temperature of the substrate was adjusted to 300°C in Example 6, an HfO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 6.

[0202] Example 8

[0203] Except that the heating temperature of the substrate was adjusted to 250°C in Example 6, an HfO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 6.

[0204] Example 9

[0205] Except that in Example 1, the inorganic precursor was replaced with CpZr, a compound represented by chemical formulas 3-5, and the film-forming material was added at a flow rate of 0.1 g / min, and the heating temperature of the substrate was adjusted to 320°C, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 1.

[0206] Chemical formula 3-5:

[0207]

[0208] Example 10

[0209] Except that the heating temperature of the substrate was adjusted to 300°C in Example 9, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 9.

[0210] Example 11

[0211] Except that the heating temperature of the substrate was adjusted to 250°C in Example 9, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 9.

[0212] Example 12

[0213] Except that in Example 6, the inorganic precursor was replaced with CpZr, a compound represented by chemical formulas 3-5, and the film-forming material was added at a flow rate of 0.1 g / min, and the heating temperature of the substrate was adjusted to 320°C, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 6.

[0214] Example 13

[0215] Except that the heating temperature of the substrate was adjusted to 300°C in Example 12, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 12.

[0216] Example 14

[0217] Except that the heating temperature of the substrate was adjusted to 250°C in Example 12, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 12.

[0218] Comparative Example 1

[0219] Except that no film-forming material was added in Example 1, an HfO2 thin film as a self-limiting atomic layer was formed using the same method as in Example 1.

[0220] Comparative Example 2

[0221] Except that no film-forming material was added in Example 2, an HfO2 thin film as a self-limiting atomic layer was formed using the same method as in Example 2.

[0222] Comparative Example 3

[0223] Except that no film-forming material was added in Example 3, an HfO2 thin film as a self-limiting atomic layer was formed using the same method as in Example 3.

[0224] Comparative Example 4

[0225] Except that no film-forming material was added in Example 6, an HfO2 thin film as a self-limiting atomic layer was formed using the same method as in Example 6.

[0226] Comparative Example 5

[0227] Except that no film-forming material was added in Example 7, an HfO2 thin film as a self-limiting atomic layer was formed using the same method as in Example 7.

[0228] Comparative Example 6

[0229] Except that no film-forming material was added in Example 8, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 8.

[0230] Comparative Example 7

[0231] Except that no film-forming material was added in Example 9, a ZrO2 thin film as a self-limiting atomic layer was formed using the same method as in Example 9.

[0232] Comparative Example 8

[0233] Except that no film-forming material was added in Example 10, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 10.

[0234] Comparative Example 9

[0235] Except that no film-forming material was added in Example 11, a ZrO2 thin film as a self-limiting atomic layer was formed in the same manner as in Example 11.

[0236] [Experimental Example]

[0237] 1) Sedimentary evaluation

[0238] The inorganic precursors in Examples 1 to 3, Examples 5 to 8, and Comparative Examples 1 to 5 were CpHf. In Example 4, the inorganic precursor was replaced with TEMAHf. In Examples 9 to 14 and Comparative Examples 6 to 7, the inorganic precursor was replaced with CpZr. Experiments were conducted, and overall, it was observed that the deposition rate decreased when the film-forming material was added before the inorganic precursor, and increased when the film-forming material was added after the inorganic precursor (refer to Table 1 and...). Figure 2 ).

[0239] As shown in Examples 1 to 6 and Comparative Examples 1 to 3, this tendency is more pronounced at low temperatures.

[0240] Furthermore, as shown in Examples 1 to 8, Comparative Examples 1 to 3, Examples 9 to 14, and Comparative Examples 6 to 7, this tendency is more pronounced in ZrO2 films.

[0241] Table 1:

[0242]

[0243] 2) Impurity reduction characteristics

[0244] The C reduction rate (%) is calculated using mathematical formula 2.

[0245] Mathematical formula 2:

[0246]

[0247] from Figure 6 As can be seen, compared with Comparative Example 1 (control group HfO2) which did not use film-forming material, the C intensity of the contaminants in the film of Examples 1 to 3, which used the film-forming material of the present invention and used an inorganic precursor as the Hf film precursor, was significantly reduced, thus confirming that the impurity reduction characteristics were excellent.

[0248] More specifically, compared to Comparative Example 1 (C(Counts / s) = 8227) which served as the control group, Example 1 (corresponding to) using CpHf as an inorganic precursor at 320°C... Figure 6 In Example 2 (a) where C intensity of the pollutant in the film was reduced by 76%, compared to Comparative Example 2 (which served as the control group), Example 2 (which used CpHf as an inorganic precursor at 300°C) showed a 76% reduction. Figure 6 In Example 3 (b) of the study, the C intensity of the pollutant in the film decreased by 66%, compared with Comparative Example 3 (C(Counts) / s) = 13745, which served as the control group. Example 3 (corresponding to Example 3) using CpHf as an inorganic precursor at 250°C... Figure 6The intensity of C, which is a contaminant in the film, was reduced by 40% in (c) of the present invention, thus confirming once again that the Hf film of the present invention has excellent impurity reduction characteristics.

[0249] 3) Thin film density

[0250] like Figure 7 As shown, it was confirmed that, compared with Comparative Example 2 (9.0 g / cm³), which served as the control group, 3 ) and Comparative Example 3 (7.7 g / cm³) 3 Compared to Example 2 (film density of 9.40 g / cm³), Example 2... 3 Example 3 (film density is 8.0 g / cm³) 3 The film density measured by X-ray reflectance measurement (XRR) was significantly increased.

[0251] Therefore, the Hf and Zr films of the present invention can improve crystallinity and ultimately improve electrical properties in integrated structures with high aspect ratios, such as DRAM capacitance.

[0252] The 7 nm thick XRD patterns deposited in Examples 1, 3, and Comparative Example 3 are shown below. Figure 9 middle.

[0253] like Figure 9 As shown, amorphous structures were observed, indicated by a very weak diffraction pattern, and no phase transition to a crystalline phase was observed at 320 degrees Celsius. For reference, it is known that very thin deposited films are predominantly amorphous; therefore, it has been confirmed that a suitable film has been fabricated.

[0254] 4) Capacitance

[0255] The electrostatic capacitance of the HfO2 thin films manufactured in Example 1 and Comparative Example 1 was measured.

[0256] Specifically, metal films are formed on the top and bottom of the dielectric film to be measured, and the metal films on the top and bottom are electrically connected to each other. The measurements are taken at a frequency of 1 MHz using a CV measurement instrument, and are shown in Table 2.

[0257] 5) Leakage current

[0258] The leakage current of the HfO2 films manufactured in Example 1 and Comparative Example 1 was measured at 3 MV / cm.

[0259] Specifically, measurements were performed using an IV parameter analyzer (model: 4200-SCS; manufacturer: Keithley) in voltage sweep mode (0-15V), and the results are shown in Table 2.

[0260] 6) Dielectric constant

[0261] The dielectric constants of the HfO2 thin films fabricated in Example 1 and Comparative Example 1 were measured.

[0262] Specifically, measurements were performed using a CV parameter analyzer (model: E4980A, LCR Meter: 20Hz~2MHz, manufacturer: Keysight Technologies) in DC-Bias Sweep Mode, and are shown in Table 2.

[0263] Table 2:

[0264] category Capacitance (F) <![CDATA[Leakage current (A / cm 2 )]]> Dielectric constant Example 1 <![CDATA[2.67×10 -10 ]]> <![CDATA[5.18×10 -8 ]]> 15.1 Comparative Example 1 <![CDATA[2.54×10 -10 ]]> <![CDATA[1.13×10 -6 ]]> 14.4

[0265] As shown in Table 2, it can be confirmed that, compared with Comparative Example 1 which did not use the film-forming material of the present invention, the dielectric constant and electrostatic capacitance of Example 1 which used the film-forming material of the present invention were improved, and the leakage current was significantly reduced.

[0266] Specifically, the leakage current is 5.18 × 10⁻⁶. -8 A / cm 2 The leakage current is below the DRAM leakage current limit, which is equivalent to an improvement of 95%. This significant reduction in leakage current is due to the improvement in thin film impurities and thin film density as confirmed above.

[0267] 7) Bottom-up conformal characteristics

[0268] The bottom-up conformal characteristics of the HfO2 films produced in Example 1 and Comparative Example 1 were confirmed.

[0269] Specifically, according to Example 1 and Comparative Example 1 of the present invention, an HfO2 thin film was deposited on a substrate having a channel structure with an aspect ratio (length / diameter) of 22.6:1 at 320°C.

[0270] Metal films were formed at the top and bottom of the HfO2 film, and TEM images of cross-sections at positions 200 nm downwards from the top and 100 nm upwards from the bottom are shown. Figure 3 middle.

[0271] like Figure 3 As shown, Example 1, which uses the film-forming material of the present invention, has a top thickness of 5.17 nm and a bottom thickness of 4.99 nm, exhibiting 97% conformal characteristics. Figure 3 In (b) of the present invention, the thickness of the top layer of Comparative Example 1, which did not use the film-forming material of the present invention, was 7.98 nm and the thickness of the bottom layer was 6.96 nm, exhibiting 87% conformal characteristics. Figure 3 (a) in the figure, thus confirming the improved bottom-up conformal characteristics.

[0272] The results of this invention do indeed demonstrate that hybrid precursors are capable of being used in ALDs designed to achieve excellent film quality, high film conformality, and outstanding electrical properties.

[0273] In the ALD process of this invention, innovative implementations of auxiliary precursors can provide a variety of opportunities in application areas such as low resistive metal gate interconnects for future technology nodes, high aspect ratio 3D metal-insulator-metal capacitors, DRAM trench capacitors, and other 3D device architectures such as 3D Gate-All-Around (GAA) and 3D NAND.

Claims

1. A film-forming composition, characterized in that, It includes film-forming materials, inorganic precursors, and reactive gases. The film-forming material includes a capping agent and a ligand exchange reactant. The capping agent is an unsaturated hydrocarbon with 2 to 15 carbon atoms formed from the film-forming material during the film-forming process. The ligand exchange reactant is hydrogen halide or halogen gas formed from the film-forming material during the film-forming process and reacting with the ligands of the inorganic precursor. The film-forming material is a branched compound, cyclic compound, or aromatic compound represented by chemical formula 1. Chemical Formula 1: A n B m X o Y i Z j Wherein, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3. The inorganic precursor is one or more film residual precursors selected from compounds represented by chemical formula 2a, compounds represented by chemical formula 2b, and compounds represented by chemical formula 2c. Chemical formula 2a: Wherein, M1 is Zr, Hf, Si, Ge, or Ti; X1, X2, and X3 are independently -NR1R2 or -OR3; R1 to R3 are independently alkyl groups having 1 to 6 carbon atoms; and n is 1 or 2. Chemical formula 2b: Wherein, M2 is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer from 0 to 5, X'1, X'2 and X'3 are independently -NR'1R'2 or -OR'3, and R'1 to R'3 are independently alkyl groups having 1 to 6 carbon atoms. Chemical formula 2c: Wherein, the M 1 Zr, Hf, Si, Ge or Ti, X 11 and X 12 Each is independently alkyl or selected from -NR 3 R 4 and -OR 5 Any of the following, the R 1 ~R 5 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein n 1 and n 2 Each is an independent integer from 0 to 5. The reactant gas is an oxidant. The film-forming material, inorganic precursor, and reactive gas form a metal oxide film on a TiN film formed on a substrate.

2. The film-forming composition according to claim 1, characterized in that, The weight ratio of the inorganic precursor to the film-forming material is 1:99 to 99:

1.

3. The film-forming composition according to claim 1, characterized in that, The composition is used for bottom-up film formation.

4. A film-forming method, characterized in that, Includes the following steps: Film-forming material is injected into the cavity and deposited on a substrate on which a TiN thin film has been formed; Inorganic precursors are implanted onto the substrate and deposited. as well as A reactive gas is injected onto the substrate, and a metal oxide film is deposited on the TiN film. The film-forming material includes a capping agent and a ligand exchange reactant. The capping agent is an unsaturated hydrocarbon with 2 to 15 carbon atoms formed from the film-forming material during the film-forming process. The ligand exchange reactant is hydrogen halide or halogen gas formed from the film-forming material during the film-forming process and reacting with the ligands of the inorganic precursor. The film-forming material is a branched compound, cyclic compound, or aromatic compound represented by chemical formula 1. Chemical Formula 1: A n B m X o Y i Z j Wherein, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3. The inorganic precursor is one or more film residual precursors selected from compounds represented by chemical formula 2a, compounds represented by chemical formula 2b, and compounds represented by chemical formula 2c. Chemical formula 2a: Wherein, M1 is Zr, Hf, Si, Ge, or Ti; X1, X2, and X3 are independently -NR1R2 or -OR3; R1 to R3 are independently alkyl groups having 1 to 6 carbon atoms; and n is 1 or 2. Chemical formula 2b: Wherein, M2 is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer from 0 to 5, X'1, X'2 and X'3 are independently -NR'1R'2 or -OR'3, and R'1 to R'3 are independently alkyl groups having 1 to 6 carbon atoms. Chemical formula 2c: Wherein, the M 1 Zr, Hf, Si, Ge or Ti, X 11 and X 12 Each is independently alkyl or selected from -NR 3 R 4 and -OR 5 Any of the following, the R 1 ~R 5 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein n 1 and n 2 Each is an independent integer from 0 to 5. The reacting gas is an oxidant.

5. A film-forming method, characterized in that, Includes the following steps: Inorganic precursors are injected into the chamber and deposited on a substrate on which a TiN thin film has been formed; Implanting and depositing a film-forming material onto the substrate; and A reactive gas is injected onto the substrate, and a metal oxide film is deposited on the TiN film. The film-forming material includes a capping agent and a ligand exchange reactant. The capping agent is an unsaturated hydrocarbon with 2 to 15 carbon atoms formed from the film-forming material during the film-forming process. The ligand exchange reactant is hydrogen halide or halogen gas formed from the film-forming material during the film-forming process and reacting with the ligands of the inorganic precursor. The film-forming material is a branched compound, cyclic compound, or aromatic compound represented by chemical formula 1. Chemical Formula 1: A n B m X o Y i Z j Wherein, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3. The inorganic precursor is one or more film residual precursors selected from compounds represented by chemical formula 2a, compounds represented by chemical formula 2b, and compounds represented by chemical formula 2c. Chemical formula 2a: Wherein, M1 is Zr, Hf, Si, Ge, or Ti; X1, X2, and X3 are independently -NR1R2 or -OR3; R1 to R3 are independently alkyl groups having 1 to 6 carbon atoms; and n is 1 or 2. Chemical formula 2b: Wherein, M2 is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer from 0 to 5, X'1, X'2 and X'3 are independently -NR'1R'2 or -OR'3, and R'1 to R'3 are independently alkyl groups having 1 to 6 carbon atoms. Chemical formula 2c: Wherein, the M 1 Zr, Hf, Si, Ge or Ti, X 11 and X 12 Each is independently alkyl or selected from -NR 3 R 4 and -OR 5 Any of the following, the R 1 ~R 5 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein n 1 and n 2 Each is an independent integer from 0 to 5. The reacting gas is an oxidant.

6. A film-forming method, characterized in that, Includes the following steps: Injecting film-forming materials and inorganic precursors into the chamber and depositing them onto the loaded substrate; and A reactive gas is injected onto the substrate, and a metal oxide film is deposited on the TiN film. The film-forming material includes a capping agent and a ligand exchange reactant. The capping agent is an unsaturated hydrocarbon with 2 to 15 carbon atoms formed from the film-forming material during the film-forming process. The ligand exchange reactant is hydrogen halide or halogen gas formed from the film-forming material during the film-forming process and reacting with the ligands of the inorganic precursor. The film-forming material is a branched compound, cyclic compound, or aromatic compound represented by chemical formula 1. Chemical Formula 1: A n B m X o Y i Z j Wherein, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3. The inorganic precursor is one or more film residual precursors selected from compounds represented by chemical formula 2a, compounds represented by chemical formula 2b, and compounds represented by chemical formula 2c. Chemical formula 2a: Wherein, M1 is Zr, Hf, Si, Ge, or Ti; X1, X2, and X3 are independently -NR1R2 or -OR3; R1 to R3 are independently alkyl groups having 1 to 6 carbon atoms; and n is 1 or 2. Chemical formula 2b: Wherein, M2 is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer from 0 to 5, X'1, X'2 and X'3 are independently -NR'1R'2 or -OR'3, and R'1 to R'3 are independently alkyl groups having 1 to 6 carbon atoms. Chemical formula 2c: Wherein, the M 1 Zr, Hf, Si, Ge or Ti, X 11 and X 12 Each is independently alkyl or selected from -NR 3 R 4 and -OR 5 Any of the following, the R 1 ~R 5 Each is independently an alkyl group having 1 to 6 carbon atoms, wherein n 1 and n 2 Each is an independent integer from 0 to 5. The reacting gas is an oxidant.

7. The film-forming method according to any one of claims 4 to 6, characterized in that, The aspect ratio of the substrate is 10:1 or higher.

8. The film-forming method according to any one of claims 4 to 6, characterized in that, The film-forming method is carried out at 200℃~800℃.

9. The film-forming method according to any one of claims 4 to 6, characterized in that, The film formation method is implemented by atomic layer deposition, chemical vapor deposition, plasma atomic layer deposition, or plasma chemical vapor deposition.

10. A thin film, characterized in that, Manufactured by the film-forming method according to any one of claims 4 to 6.

11. The thin film according to claim 10, characterized in that, The thin film is an anti-diffusion film, an etch-stop film, a charge trap, a selective area deposition film, or a bottom-up film.

12. A semiconductor substrate, characterized in that, Includes the thin film as described in claim 10.

13. The semiconductor substrate according to claim 12, characterized in that, The semiconductor substrate is a low-resistance metal gate interconnect, a high aspect ratio 3D metal-insulator-metal capacitor, a DRAM channel capacitor, a 3D all-around gate, or a 3D NAND.

14. A semiconductor device, characterized in that, Includes the semiconductor substrate as described in claim 12.

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