Film-forming material, film-forming composition, film-forming method using the same, and semiconductor device manufactured therefrom

Abstract

The present invention relates to a film formation material, a film formation composition, a film formation method using the same, and a semiconductor device manufactured therefrom. According to the present invention, there are provided a film formation material, a film formation composition, a film formation method using the same, and a semiconductor device manufactured therefrom, which provide a conformal thin film even when a thin film is formed on a substrate having a complex structure by lowering the growth rate, reduce impurities in the thin film, greatly improve the density of the thin film, and greatly reduce leakage current that occurs due to oxidation of the lower electrode in conventional high-temperature processes.

Description

[Technical Field]

[0001] 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 using the same. More specifically, the present invention relates to a film-forming material, a film-forming composition, a method for forming a high-purity, conformal, and dense thin film using a bottom-up method by controlling the thin film formation rate through the film-forming material contained in the film-forming composition and inducing ligand exchange with components that are not desired to remain on the substrate. The present invention also relates to a film-forming method using the same and a semiconductor device manufactured using the same, which improves the quality of the film formed through a chemical reaction with the substrate, thereby improving crystallinity, and reducing the impurity concentration in the thin film, thereby reducing leakage current generation. [Background technology]

[0002] In recent years, in the field of semiconductor technology, the pursuit of more advanced technology through the miniaturization of semiconductor devices has led to active research into suitable materials and process technologies. In particular, there has been a great deal of research into the manufacturing process of oxide thin films, such as TiO2, ZrO2, HfO2, and Al2O3, which are high-k materials used in capacitors for dynamic random access memories (DRAMs).

[0003] Metal organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) are commonly used processes for manufacturing metal oxide thin films in semiconductor manufacturing, but there are various limitations when forming metal oxide thin films using chemical vapor deposition and atomic layer deposition. First, with the miniaturization of semiconductor devices and high-temperature processes, leakage current occurs due to oxidation of the bottom electrode, and the crystallinity of the thin film is low at limited temperatures, limiting capacitance.

[0004] DRAM capacitors have high capacitance and -7 A / cm 2This is a key variable in providing thin dielectric films that meet the stringent requirements of DRAM cells, which require a low leakage current, especially as leakage current continues to decrease (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 that when an 8.6 nm thick amorphous thin film and a monoclinic thin film were fabricated through ALD of HfO2 using CpHf(NMe2)3 and ozone at 250 to 400 °C and post-annealed from 500 °C, the thermal conductivity was 1 × 10 -7 A / cm 2 reported the strength of the leakage current of (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 known that bulk-related leakage conduction mechanisms, such as trap-assisted tunneling (TAT) or Poole-Frenkel (PF) emission, dominate in materials such as ZrO2 and HfO2, rather than interface-related leakage current conduction (WY Choi, G. Yoon, WY Chung, Y. Cho, S. SHin and KHAhn, Micromachines 10, 256 (2019)). In particular, the carrier conduction mechanism is known to be significantly affected by the bulk properties of defects in the dielectric film, such as grain boundaries, internal impurities (e.g., oxygen deficiency), and external impurities incorporated into the thin film during the deposition process.

[0007] Therefore, rather than using different dielectric materials with higher dielectric constants or metal electrodes with different work functions, techniques that reduce the source of these defects in bulk ZrO2 and HfO2 would be more effective.

[0008] The thin film of the present invention induces ligand exchange with components that are not desired to remain on the substrate through a film-forming material that simultaneously provides a blocking agent and a ligand exchange reactant, thereby improving film quality and film conformality, reducing leakage current, and ensuring the reliability of semiconductor devices even at low temperatures such as 250°C. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to provide a conformal thin film by reducing the growth rate, even when forming a thin film on a substrate with a complex structure, while reducing impurities in the thin film, significantly improving the density of the thin film, and reducing leakage current.

[0010] Another object of the present invention is to ensure the reliability of semiconductor devices by providing a thin film having a high dielectric constant (high-k) under low temperature conditions. [Means for solving the problem]

[0011] To achieve the above object, the present invention provides a film-forming material comprising a blocking agent and a ligand exchange reagent.

[0012] The blocking agent may be an unsaturated hydrocarbon having 2 to 5 carbon atoms formed from the deposition material during the deposition process.

[0013] The ligand exchange reactant may be a hydrogen halide or halogen gas that is formed from the deposition material during the deposition process and that exchanges with the ligands of the inorganic precursor.

[0014] The film-forming material may be a branched, cyclic, or aromatic compound represented by the following chemical formula 1:

[0015] [Chemical formula 1] AnBmXoYiZj

[0016] (A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are integers from 0 to 3.)

[0017] The present invention also provides bottom-up thin film compositions that include pulse precursors.

[0018] The pulsed precursor may be a hybrid precursor containing the above-mentioned film-forming material (hereinafter also referred to as organic precursor) and an inorganic precursor.

[0019] The inorganic precursor may include one or more elements selected from the group consisting of 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.

[0020] The inorganic precursor may be at least one thin film residual precursor selected from the group consisting of a compound represented by the following Formula 2a; a compound represented by the following Formula 2b; and a compound represented by the following Formula 2c:

[0021] [Chemical formula 2a] JPEG0007812872000001.jpg97115

[0022] (M1 is Zr, Hf, Si, Ge, or Ti; X1, X2, and X3 are independently —NR1R2 or —OR3; R1 to R3 are independently an alkyl group having 1 to 6 carbon atoms; and n is 1 or 2.)

[0023] [Chemical formula 2b] JPEG0007812872000002.jpg115116

[0024] (M 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 -NR1R2 or -OR3; and R'1 to R'3 are independently an alkyl group having 1 to 6 carbon atoms.)

[0025] [Chemical formula 2c] JPEG0007812872000003.jpg127115

[0026] (M1 is Zr, Hf, Si, Ge or Ti, and X 11 and X 12 are each independently an alkyl group or any one selected from the group consisting of -NR3R4 and -OR5, and R1 to R5 are each independently an alkyl group having 1 to 6 carbon atoms, and n 1 and n 2 are each independently an integer from 0 to 5.

[0027] The inorganic precursor and the film-forming material may have a weight ratio of 1:99 to 99:1.

[0028] The composition may include a pulse of a reactive gas.

[0029] The pulse of reactive gas may be an oxidizer pulse, a nitridizer pulse, or a reducer pulse.

[0030] The deposition composition can be a bottom-up deposition or selective area deposition composition.

[0031] The present invention also provides Injecting the film forming material into the chamber and depositing it on the loaded substrate; injecting and depositing an inorganic precursor onto the substrate; and injecting a pulse of a reactive gas onto the substrate to deposit;

[0032] The inorganic precursor contains one or more substances selected from the group consisting of 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.

[0033] The present invention also provides Injecting an inorganic precursor into the chamber and depositing it on the loaded substrate; Injecting and depositing the film-forming material onto the substrate; and injecting a pulse of a reactive gas onto the substrate to deposit;

[0034] The inorganic precursor contains one or more substances selected from the group consisting of 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.

[0035] The present invention also provides Injecting the film-forming material and inorganic precursor into the chamber and depositing them on the loaded substrate; and injecting a pulse of a reactive gas onto the substrate to deposit;

[0036] The inorganic precursor contains one or more substances selected from the group consisting of 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.

[0037] The film formation method may include depositing a blocking agent and a ligand exchange reactant formed from the film formation material on a substrate; and exchanging the ligand of the inorganic precursor with the ligand exchange reactant.

[0038] The inorganic precursor may remain on the substrate and the deposition material may not remain on the substrate.

[0039] The substrate may have an aspect ratio of 10:1 or greater.

[0040] The deposition material and the inorganic precursor may be provided in pulses.

[0041] The film formation method can be carried out at a temperature of 200 to 800°C.

[0042] The reactive gas pulse may be an oxidizing, reducing or nitriding agent pulse.

[0043] The film formation method may be performed by atomic layer deposition, chemical vapor deposition, plasma-enhanced atomic layer deposition, or plasma-enhanced chemical vapor deposition.

[0044] The deposition method may be bottom-up deposition.

[0045] The film formation method can form a metal oxide thin film, a metal nitride thin film, a metal thin film, or a thin film having selective regions of two or more of these thin films.

[0046] The present invention also provides a method for forming a bottom-up thin film, comprising the steps of injecting a bottom-up thin film composition containing the above-described film-forming material and a pulse precursor into a chamber, and bottom-up depositing the inorganic precursor on a surface of a substrate loaded in the chamber.

[0047] The bottom-up deposition of the inorganic precursor on the substrate may include injecting a pulse of the deposition material onto the substrate and purging; injecting a pulse of the deposition material onto the substrate and purging; and injecting a pulse of a reactive gas onto the substrate and purging.

[0048] The bottom-up deposition of the inorganic precursor on the substrate may include injecting a pulse of the inorganic precursor onto the substrate and purging; injecting a pulse of the deposition material onto the substrate and purging; and injecting a pulse of a reactive gas onto the substrate and purging.

[0049] The bottom-up deposition of the inorganic precursor on the substrate may include injecting a pulse of the deposition material onto the substrate and purging; injecting a pulse of the deposition material onto the substrate and purging; injecting a pulse of a reactive gas onto the substrate and purging; and injecting a pulse of the deposition material onto the substrate and purging.

[0050] The bottom-up deposition of the inorganic precursor on the substrate may include simultaneously injecting the inorganic precursor and the organic precursor onto the substrate and purging; and injecting a pulse of a reactive gas onto the substrate and purging.

[0051] The substrate may have an aspect ratio of 10:1 or greater.

[0052] The deposition material and the inorganic precursor may be provided in pulses.

[0053] The film formation method can be carried out at a temperature of 200 to 800°C.

[0054] The reactive gas pulse may be an oxidizing, reducing or nitriding agent pulse.

[0055] The inorganic precursor may remain on the substrate, and the deposition material may not substantially remain on the substrate (become "unremained").

[0056] The bottom-up thin film formation method may be performed by atomic layer deposition, chemical vapor deposition, plasma-enhanced atomic layer deposition, or plasma-enhanced chemical vapor deposition.

[0057] The bottom-up thin film formation method can form a metal oxide thin film, a metal nitride thin film, a metal thin film, a non-metal oxide thin film, a non-metal nitride thin film, other dielectric thin films, or a thin film having selective regions of two or more of these thin films. Here, "non-metal" refers to a material other than metal as known in the art, such as silicon.

[0058] The present invention also provides a semiconductor substrate manufactured by the above-mentioned film formation method.

[0059] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, 3D gate-all-around (GAA) or 3D NAND.

[0060] The present invention also provides a semiconductor device comprising the semiconductor substrate described above. [Effects of the Invention]

[0061] The present invention has the effect of providing a film-forming material that can simultaneously provide a blocking agent and a ligand exchange reaction agent during the film-forming process.

[0062] According to the present invention, there is provided a film-forming composition that induces ligand exchange with components that are not desired to remain on the substrate through the film-forming material, thereby providing a conformal thin film even when forming a thin film on a substrate having a complex structure.

[0063] According to the present invention, there is provided a film-forming composition that can more effectively remove process by-products generated during film formation and unwanted components that do not remain, reduce the deposition rate to appropriately lower the film formation rate, and improve the crystallinity of the thin film, thereby improving the quality of the thin film.

[0064] According to the present invention, there is an advantage in that a bottom-up thin film composition is provided that provides a conformal thin film by a bottom-up method even when forming a thin film on a substrate having a complex structure.

[0065] According to the present invention, there is an effect of providing a thin film composition that can more effectively remove process by-products during bottom-up thin film formation, reduce the deposition rate, appropriately lower the thin film growth rate, and improve the crystallinity of the thin film, thereby improving the quality of the thin film.

[0066] According to the present invention, it is possible to provide a film-forming composition that reduces impurities in a thin film, thereby significantly improving the density of the thin film and reducing leakage current that occurs due to oxidation of a lower electrode in a conventional high-temperature process, and further, it is possible to provide a film-forming method using the same and a semiconductor device manufactured using the same. [Brief explanation of the drawings]

[0067] [Figure 1] 1 is a diagram schematically illustrating a film formation cycle using a film formation composition according to the present invention, in which the left-hand drawing shows a film formation cycle in which a film formation material is added and then an inorganic precursor is added (hereinafter also referred to as the first step), and the right-hand drawing shows a film formation cycle in which an inorganic precursor of the film formation composition is added and then a film formation material is added (hereinafter also referred to as the second step). [Figure 2] 1 is a GPC analysis graph showing deposition rates for bottom-up thin films of Examples 1 to 3 and 6 to 8 of the present invention and bottom-up thin films of Comparative Examples 1 to 6 (Ref. HfO2). [Figure 3]TEM photographs of cross sections of HfO thin films deposited at 320°C on a substrate having a trench structure with an aspect ratio (length / diameter) of 22.6:1 according to Example 1 of the present invention and Comparative Example 1, taken at a point 200 nm below the top and a point 100 nm above the bottom. [Figure 4] FIG. 1 is a flow chart outlining a first step in which a blocking agent and a ligand exchange reactant generated during the film formation process are deposited on a substrate from a film formation material according to Example 1 of the present invention, and then an inorganic precursor is adsorbed. [Figure 5] FIG. 4 is a flow chart outlining the process in which, after the blocking agent and the ligand exchange reactant are deposited on the substrate, the inorganic precursor is adsorbed from the product of the first step, and then the dialkylamine and Cp, which are the ligands of the inorganic precursor, are exchanged with the ligand exchange reactant, respectively, to produce a metal oxide film from the reactant gas. [Figure 6] 1 is a SIMS analysis graph showing the reduction rates of carbon (C), iodine (I), and the like depending on the depth of bottom-up thin films fabricated at deposition temperatures of 320°C (graph a, Example 1 and Comparative Example 1), 300°C (graph b, Example 2 and Comparative Example 2), and 250°C (graph c, Example 3 and Comparative Example 3). [Figure 7] 1 is a graph showing the analysis of film density of bottom-up thin films manufactured at deposition temperatures of 320° C., 300° C., and 250° C. for Examples 1 to 3 of the present invention and Comparative Examples 1 to 3. [Figure 8] 1 is an XPS analysis graph showing the component contents (atomic %) according to the depth of bottom-up thin films prepared at a deposition temperature of 250° C. in Example 3 of the present invention and Comparative Example 3. [Figure 9] 1 is an analysis graph of XRD patterns of bottom-up thin films prepared at a deposition temperature of 250° C. in Example 3 of the present invention and Comparative Examples 1 and 3. DETAILED DESCRIPTION OF THE INVENTION

[0068] The film-forming composition, bottom-up thin film composition, film-forming method using the same, and semiconductor substrates and semiconductor devices manufactured therefrom will be described in detail below.

[0069] Unless otherwise specified, the term "blocking agent" as used herein refers to an additive that is adsorbed onto a substrate competitively with inorganic precursors to control the film formation rate or inhibit dense adsorption of the inorganic precursors. Specific examples can be seen in Figure 4(b) below. Figure 4 below is a process diagram that outlines the first step in which the blocking agent and ligand exchange reactant generated from the film formation material during the film formation process are deposited on the substrate, and then the inorganic precursor is adsorbed. As shown in Figure 4 below, the film formation material injected onto the substrate in (a) is separated into the blocking agent and ligand exchange reactant as shown in (b), and each is weakly adsorbed on the substrate, thereby reducing the number of sites where the inorganic precursor provided in (c) can be adsorbed.

[0070] The term "ligand exchange reactant" as used herein refers to an additive that undergoes an exchange reaction with the ligand of an inorganic precursor, unless otherwise specified. Specific examples can be seen in Figures 5(a) and 5(b) below. Figure 5 below is a process diagram that schematically illustrates the process in which, after a blocking agent and a ligand exchange reactant are deposited on a substrate in Figure 4, the product of the first step in which an inorganic precursor is adsorbed undergoes ligand exchange with the dialkylamine and Cp, which are the ligands of the inorganic precursor, by the ligand exchange reactant, respectively, to produce a metal oxide film from the reactant gas.

[0071] As shown in Figure 5 below, after the aforementioned blocking agent and ligand exchange reactant are deposited on the substrate, the product of the first step (corresponding to Figure 4(d) or Figure 5(a)) in which the inorganic precursor is adsorbed undergoes an exchange reaction with dialkylamine, which is the ligand of the inorganic precursor (corresponding to Figure 5(a)), and an exchange reaction with Cp, another ligand of the inorganic precursor (corresponding to Figure 5(b)), leaving halogen at the position, which then reacts with the injected reactant gas to produce a metal oxide film.

[0072] As used herein, unless otherwise specified, the term "bottom-up" refers to growth from the bottom on a substrate having a trench structure, where the substrate having a trench structure may, for example, have an aspect ratio of 10:1 or greater, or 20:1 or greater.

[0073] The aspect ratio, unless otherwise specified, refers to the length / diameter (L / D) ratio of the trench structure, where length and diameter are defined as commonly used in the art.

[0074] The inventors of the present invention have confirmed that when a film is formed on the surface of a substrate loaded into a chamber using a film formation composition containing an inorganic precursor and a film formation material, the growth rate of the top and bottom of the thin film formed after deposition is significantly reduced even at a low temperature such as 250°C, resulting in significantly improved conformal properties in a trench structure with a high aspect ratio. Furthermore, contrary to expectations, the inventors have confirmed that the amount of residual carbon and iodine is reduced, significantly improving the density and impurities of the thin film. Based on this, they have conducted further research and have completed the present invention.

[0075] The film formation method is one embodiment and may include the steps of vaporizing an inorganic precursor and a film formation material, separately or simultaneously, and adsorbing them onto a surface of a substrate loaded into a chamber; purging the interior of the chamber with a purge gas; supplying a reaction gas into the chamber; and purging the interior of the chamber with a purge gas. In this case, even if the film formation rate is appropriately reduced and the deposition temperature is low during film formation, the density, crystallinity, conformal properties, and dielectric properties of the thin film are improved, and leakage current is effectively reduced, thereby significantly improving film quality.

[0076] In a preferred embodiment, the film formation method involves injecting a bottom-up thin film composition containing pulsed precursors into a chamber and depositing the composition on the surface of a loaded substrate. The pulsed precursors may include an inorganic precursor and an organic precursor, and the inorganic precursor and the organic precursor may be co-injected onto the substrate, followed by injecting a pulse of a reactive gas to deposit the composition. In this case, the thin film growth rate is appropriately reduced, and even if the deposition temperature during thin film formation is low, the density, crystallinity, conformal properties, and dielectric properties of the bottom-up thin film are improved, and leakage current is effectively reduced, resulting in significantly improved film quality.

[0077] In another preferred embodiment, the film formation method may include the steps of injecting a film formation material into a chamber and depositing it on a loaded substrate; injecting an inorganic precursor onto the substrate and depositing it; and injecting pulses of a reactive gas onto the substrate and depositing it. In this case, even if the film formation rate is appropriately reduced and the deposition temperature during film formation is low, the density, crystallinity, conformal properties, and dielectric properties of the thin film are improved, leakage current is effectively reduced, and film quality is significantly improved.

[0078] In a preferred embodiment, the film formation method may include the steps of injecting an inorganic precursor into a chamber and depositing it on a loaded substrate; injecting a film formation material onto the substrate and depositing it; and injecting pulses of a reactive gas onto the substrate and depositing it. In this case, the film formation rate is appropriately reduced, and even if the deposition temperature during film formation is low, the density, crystallinity, conformal properties, and dielectric properties of the thin film are improved, leakage current is effectively reduced, and film quality is significantly improved.

[0079] In a preferred embodiment, the film formation method may include the steps of injecting and depositing a film formation material and an inorganic precursor onto the surface of a substrate loaded into a chamber; and injecting pulses of a reactive gas onto the substrate to deposit the material. In this case, even if the film formation rate is appropriately reduced and the deposition temperature during film formation is low, the density, crystallinity, conformal properties, and dielectric properties of the thin film are improved, leakage current is effectively reduced, and film quality is significantly improved.

[0080] In a preferred embodiment, the deposition method may include the steps of injecting a deposition material onto a substrate and purging; injecting an inorganic precursor onto the substrate and purging; injecting a pulse of a reactive gas onto the substrate, purging, and depositing the inorganic precursor; and injecting the deposition material onto the substrate and purging. In this case, even if the deposition rate is appropriately reduced and the deposition temperature during deposition is low, the density, crystallinity, conformal properties, and dielectric properties of the thin film are improved, leakage current is effectively reduced, and film quality is greatly improved.

[0081] The thin film produced by the film formation method may be a bottom-up thin film, characterized in that the inorganic precursor remains and is deposited to form the thin film, but the film-forming material does not remain.

[0082] The inorganic precursor, film forming material, reaction gas, and purge gas can be independently delivered into the chamber, preferably by VFC, DLI, or LDS, and more preferably by LDS.

[0083] The chamber can be, but is not limited to, a CVD chamber or an ALD chamber.

[0084] In one embodiment of the present invention, the film-forming material may include a blocking agent and a ligand exchange reagent.

[0085] As shown in FIG. 4(b) above, the blocking agent may be an unsaturated hydrocarbon having 2 to 15 carbon atoms formed from the film-forming material during the film-forming process. Preferably, the blocking agent is an unsaturated hydrocarbon having 2 to 15 carbon atoms and a tertiary structure, which can maximize the blocking effect of blocking the approach of the inorganic precursor to be adsorbed onto the substrate.

[0086] As shown in Figures 5(a) and (b) above, the ligand exchange reactant may be a hydrogen halide or halogen gas that is formed from the film formation material during the film formation process and undergoes an exchange reaction with the ligand of the inorganic precursor. Using a hydrogen halide is preferable because it can simultaneously maximize the blocking effect of blocking the approach of the inorganic precursor to adsorb onto the substrate and the effect of performing an exchange reaction with the ligand of the inorganic precursor adsorbed nearby.

[0087] Here, F, Cl, Br, or I can be used as the halogen, and it may be preferable to use I or Br when taking into consideration the reactivity with the reaction gas to be used in the future.

[0088] The film-forming material used in the present invention refers to a substance that is substantially unreactive with the inorganic precursor described below and that is "unremained" (does not substantially remain) in the thin film. One example is a branched, cyclic, or aromatic compound represented by the following chemical formula 1. In this case, the film-forming material acts as a "unremained" (does not substantially remain) precursor in the thin film, thereby effectively achieving the effects aimed at by the present invention and providing a high dielectric constant.

[0089] [Chemical formula 1] AnBmXoYiZj

[0090] (A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not equal to each other, n is an integer from 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are integers from 0 to 3.)

[0091] Unless otherwise specified, the term "unremained" used in the present invention refers to the case where the C element is present at less than 0.1 atomic % (atom %) and the N element is present at less than 0.1 atomic % (atom %) when analyzed by XPS.

[0092] The film-forming material is preferably a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, when a compound with a purity of less than 99% is used, impurities may be formed, and it is preferable to use a substance with a purity of 99% or more.

[0093] For example, when the film-forming material is tert-butyl iodide, the blocking agent may be 2-methylpropene and the ligand exchange reactant may be hydrogen iodide.

[0094] The film forming material may be supplied in a pulsed manner using a Vapor Flow Controller (VFC) and / or a Liquid Delivery System (LDS), and in this case, the pulsed manner may be any pulsed state commonly used in the art.

[0095] In one embodiment of the present invention, the deposition composition may include an inorganic precursor along with the deposition material.

[0096] In one embodiment of the present invention, the film-forming composition may be a bottom-up thin film composition.

[0097] In one embodiment of the present invention, the bottom-up thin film composition may include a pulse precursor.

[0098] In the present 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), and in this case, the term "pulsed" may refer to any pulse state commonly used in the art.

[0099] An example of the pulsed precursor may be a hybrid precursor comprising an inorganic precursor and an organic precursor.

[0100] The inorganic precursor used in the present invention refers to a material that can remain in the thin film and help improve conductivity, and can be, for example, a material represented by the following Chemical Formula 2.

[0101] [Chemical formula 2] MxLy

[0102] wherein x is an integer from 1 to 3, M may be selected from the group consisting of 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; and y is an integer from 1 to 6, and each L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a combination of two or more ligands selected from the group consisting of H, C, N, O, F, P, S, Cl, and Br.

[0103] In this case, the effect aimed at by the present invention is well exhibited, and there is an advantage in that it has a high dielectric constant.

[0104] In a preferred embodiment, the inorganic precursor is a thin film residual precursor selected from the group consisting of a compound represented by the following formula 2a; a compound represented by the following formula 2b; and a compound represented by the following formula 2c, which is preferred in terms of thermal stability and reactivity:

[0105] [Chemical formula 2a] JPEG0007812872000004.jpg97115

[0106] (M1 is Zr, Hf, Si, Ge, or Ti; X1, X2, and X3 are independently —NR1R2 or —OR3; R1 to R3 are independently an alkyl group having 1 to 6 carbon atoms; and n is 1 or 2.)

[0107] [Chemical formula 2b] JPEG0007812872000005.jpg115116

[0108] (M 2 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 of 0 to 5, X'1, X'2 and X'3 are independently -NR1R2 or -OR3, and R'1 to R'3 are independently an alkyl group having 1 to 6 carbon atoms.

[0109] [Chemical formula 2c] JPEG0007812872000006.jpg127115

[0110] (M 1 is Zr, Hf, Si, Ge or Ti, and X 11 and X 12 are each independently an alkyl group or any one selected from the group consisting of -NR3R4 and -OR5, 1 ~R 5are each independently an alkyl group having 1 to 6 carbon atoms, 1 and n 2 are each independently an integer from 0 to 5.

[0111] The inorganic precursor and the deposition material may have a weight ratio of 1:99 to 99:1, a weight ratio of 1:90 to 90:1, a weight ratio of 1:85 to 85:1, or a weight ratio of 1:80 to 80:1.

[0112] The composition includes a pulse of a reactive gas, which may be one or more selected from an oxidizing agent, a nitriding agent, and a reducing agent.

[0113] The oxidizing agent, nitriding agent, and reducing agent may be substances commonly used in the art. For example, the oxidizing agent may be O3, O2, or a mixture thereof, the nitriding agent may be NH3, N2H2, N2, or a mixture thereof, and the reducing agent may be H2, etc., but is not limited thereto.

[0114] The film-forming method of the present invention includes depositing an inorganic precursor on a substrate using a film-forming material.

[0115] In the film formation method of the present invention, the step of depositing the inorganic precursor on the substrate may, for example, include the steps of depositing a blocking agent and a ligand exchange reactant formed from a film formation material on the substrate; and depositing the inorganic precursor on the substrate by exchanging the ligand of the inorganic precursor with the ligand exchange reactant.

[0116] In the film formation method of the present invention, the step of depositing the inorganic precursor on the substrate may preferably include the steps of depositing a blocking agent and a ligand exchange reactant formed from a film formation material on the substrate; causing the ligand exchange reactant to exchange with the ligand of the inorganic precursor; and injecting a pulse of a reaction gas onto the substrate to deposit the inorganic precursor.

[0117] Here, the inorganic precursor may be added after the injection of the film-forming material, before the injection of the film-forming material, or simultaneously with the injection of the film-forming material.

[0118] In the bottom-up film formation method of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may preferably include the steps of injecting a pulse of the film formation material onto the substrate and purging; injecting a pulse of the inorganic precursor onto the substrate and purging; and injecting a pulse of a reaction gas onto the substrate and purging.

[0119] In this case, when the inorganic precursor is introduced after the film-forming material is introduced, a blocking reaction and a ligand exchange reaction can be carried out according to the flow charts shown in FIGS. 4 and 5 below.

[0120] In the bottom-up film formation method of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may, as another preferred example, include the steps of injecting a pulse of the inorganic precursor onto the substrate and purging; injecting a pulse of the film formation material onto the substrate and purging; and injecting a pulse of the reaction gas onto the substrate and purging.

[0121] In addition, in the bottom-up film formation method of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may, as another preferred example, include the steps of injecting a pulse of the film formation material onto the substrate and purging; injecting a pulse of the inorganic precursor onto the substrate and purging; injecting a pulse of a reaction gas onto the substrate and purging; and injecting a pulse of the film formation material onto the substrate and purging.

[0122] In addition, in the bottom-up film formation method of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may, as another preferred example, include the steps of simultaneously injecting a pulse of the inorganic precursor and a pulse of the film formation material onto the substrate and purging; and the steps of injecting a pulse of a reaction gas onto the substrate and purging.

[0123] The substrate may be a trench-structured substrate having an aspect ratio of 10:1 or more, or 20:1 or more.

[0124] In the film formation method, the deposition temperature is, for example, 200 to 800°C, a specific example is 200 to 600°C, preferably 250 to 450°C, and specific examples are 250 to 420°C, 250 to 320°C, 380 to 420°C, or 400 to 450°C, and within this range, there is an advantage that the thin film quality and step coverage are greatly improved.

[0125] For example, the film formation method may use a reducing agent, a nitriding agent, or an oxidizing agent as a reactive gas, and if necessary, different reactive gases may be applied to selected regions and the remaining regions.

[0126] The film formation method may be, for example, atomic layer deposition or chemical vapor deposition, and may be plasma atomic layer deposition or plasma chemical vapor deposition, if necessary.

[0127] The deposition method may, for example, form a metal oxide thin film, a metal nitride thin film, a metal thin film, a non-metal oxide thin film, a non-metal nitride thin film, another dielectric thin film, or a thin film having selective regions of two or more of these thin films.

[0128] According to one embodiment of the present invention, it is possible to provide a thin film that is manufactured by the above-described film formation method.

[0129] The thin film can be used as a diffusion barrier, an etch stop, a charge trap, a selective area deposition film, a bottom-up thin film, and the like.

[0130] According to one embodiment of the present invention, there is provided a semiconductor substrate manufactured by the above-described film formation method.

[0131] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, 3D Gate-All-Around (GAA) or 3D NAND.

[0132] Furthermore, according to another embodiment of the present invention, there is provided a semiconductor device including the semiconductor substrate described above.

[0133] For example, a capacitor including a thin film according to the present invention may be provided by stacking two or more layers, and the inorganic precursors constituting each layer may be different in type, or may be the same type, if necessary.

[0134] For example, a capacitor may be formed by sequentially forming a lower electrode, a dielectric film, and a second electrode on a semiconductor substrate.

[0135] In this case, the lower electrode may be a storage electrode of a DRAM device or other device or an electrode of a decoupling capacitor.

[0136] For example, the lower electrode may be manufactured in a cylindrical or pillar shape that can secure a large surface area, and may be formed as a conductive layer or a metal layer.

[0137] The dielectric film may be a metal oxide film, and when deposited using the film-forming composition according to the present invention, it has the advantage of having a uniform thickness and suitable adhesion even when formed on a lower electrode having a lower step or topology.

[0138] The upper electrode formed on the dielectric layer may be made of the same conductive or metal layer as the lower electrode.

[0139] In the following, preferred embodiments and drawings are presented to aid in understanding the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope of the scope and technical idea of ​​the present invention. Naturally, such changes and modifications also fall within the scope of the appended claims.

[0140] [Example] Example 1 Using the thin film manufacturing cycle shown in the left diagram of Figure 1 below, a bottom-up HfO2 thin film was deposited on a SiO2 substrate having a trench structure with an aspect ratio of 22.6:1 (length:diameter).

[0141] The left side of FIG. 1 corresponds to an experiment of pulsing an inorganic precursor after pulsing a film-forming material in a bottom-up thin film composition according to the present invention, and is referred to as the first step.

[0142] Specifically, the cycle includes injecting a film forming material pulse for 3 seconds followed by purging for 6 seconds, injecting an inorganic precursor pulse for 3 seconds followed by purging for 6 seconds, and then injecting a reactive gas pulse for 3 seconds followed by purging for 6 seconds.

[0143] The HfO2 bottom-up thin film was deposited using a 12-inch ALD system equipped with a shower head.

[0144] The inorganic precursor was prepared as CpHf, a compound represented by the following formula 3-1: CpHf was purchased from Sigma and used without purification.

[0145] [Chemical formula 3-1] JPEG0007812872000007.jpg115125

[0146] The film-forming material was prepared as TBI, a compound represented by the following chemical formula 3-2. The TBI was synthesized by the applicant and purified to a purity of 99.9% before use.

[0147] [Chemical formula 3-2] JPEG0007812872000008.jpg125138

[0148] The prepared film-forming material was placed in a canister and supplied to a vaporizer heated to 90°C at a flow rate of 0.01 g / min using an LMFC (Liquid Mass Flow Controller) at room temperature. The prepared CpHf was placed in another canister and supplied to a separate vaporizer heated to 170°C at a flow rate of 0.1 g / min.

[0149] The deposition material vaporized in a vaporizer was introduced into a deposition chamber containing a Si wafer with 100 nm of SiO2 grown on it and 20 nm of TiN grown on top. Argon gas was then supplied at 300 sccm for 6 seconds to purge the chamber. The substrate on which the metal oxide film was to be formed was heated to 320°C, while the pressure in the reaction chamber was controlled at 0.74 Torr.

[0150] Next, CpHf vaporized in a vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 300 sccm for 6 seconds to perform argon purging. The substrate on which the metal oxide film was to be formed was heated to 320°C, and the pressure in the reaction chamber was controlled at 0.74 Torr.

[0151] Next, 1000 sccm of ozone was introduced into the reaction chamber as a reactive gas for 3 seconds, followed by argon purging for 6 seconds. The substrate on which the metal oxide film was to be formed was heated to 320°C, and the pressure inside the reaction chamber was controlled at 0.74 Torr.

[0152] This process was repeated 100 times to form a self-limiting atomic layer HfO2 thin film.

[0153] <Example 2> In Example 1, a HfO2 thin film was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 300°C.

[0154] Example 3 In Example 1, a HfO2 thin film was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 250°C.

[0155] Example 4 A HfO thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 1, except that the inorganic precursor in Example 1 was replaced with TEMAHf (Tetrakis(ethylmethylamino)Hafnium), a compound represented by the following chemical formula 3-3.

[0156] [Chemical formula 3-3] JPEG0007812872000009.jpg109115

[0157] <Example 5> A self-limiting atomic layer HfO2 thin film was formed in the same manner as in Example 1, except that the film forming material was replaced with TBB, a compound represented by the following chemical formula 3-4.

[0158] The TBB was synthesized by the applicant and purified to 99.9% purity before use.

[0159] [Chemical formula 3-4] JPEG0007812872000010.jpg108119

[0160] Example 6 The same steps as in Example 1 were repeated, except that the thin film production cycle shown in the left drawing of FIG. 1 used in Example 1 was changed to the thin film production cycle shown in the right drawing of FIG.

[0161] Specifically, a bottom-up HfO2 thin film was deposited on a SiO2 substrate having a trench structure with an aspect ratio of 22.6:1 (length:diameter) using the deposition cycle shown in the diagram on the right side of Figure 1.

[0162] The right side of FIG. 1 corresponds to an experiment of pulsing the film-forming material after pulsing the inorganic precursor according to the present invention, and is referred to as the second step.

[0163] Specifically, the cycle consisted of injecting a pulse of inorganic precursor for 3 seconds, followed by purging for 6 seconds, injecting a pulse of film-forming material for 3 seconds, followed by purging for 6 seconds, and then injecting a pulse of reactive gas for 3 seconds, followed by purging for 6 seconds. The substrate on which the metal oxide film was to be formed was heated to 320°C, and the pressure in the reaction chamber was controlled at 0.74 Torr.

[0164] Example 7 In Example 6, a HfO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 300°C.

[0165] Example 8 In Example 6, a HfO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 250°C.

[0166] Example 9 A self-limiting atomic layer ZrO thin film was formed in the same manner as in Example 1, except that the inorganic precursor in Example 1 was replaced with CpZr, a compound represented by the following chemical formula 3-5, the film formation material was fed at a flow rate of 0.1 g / min, and the substrate heating temperature was adjusted to 320°C.

[0167] [Chemical formula 3-5] JPEG0007812872000011.jpg115119

[0168] Example 10 In Example 9, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that the heating temperature of the substrate was adjusted to 300°C.

[0169] Example 11 In Example 9, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that the heating temperature of the substrate was adjusted to 250°C.

[0170] Example 12 In Example 6, a ZrO thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 1, except that the inorganic precursor in Example 6 was replaced with CpZr, which is a compound represented by the following chemical formula 3-5, the film formation material was fed at a flow rate of 0.1 g / min, and the substrate heating temperature was adjusted to 320°C.

[0171] Example 13 In Example 12, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 12, except that the heating temperature of the substrate was adjusted to 300°C.

[0172] Example 14 In Example 12, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 12, except that the heating temperature of the substrate was adjusted to 250°C.

[0173] <Comparative Example 1> A HfO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 1, except that no film-forming material was added.

[0174] <Comparative Example 2> In Example 2, a HfO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 2, except that no film-forming material was added.

[0175] <Comparative Example 3> In Example 3, a HfO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 3, except that no film-forming material was added.

[0176] <Comparative Example 4> In Example 6, a HfO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 6, except that no film-forming material was added.

[0177] <Comparative Example 5> In Example 7, a HfO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 7, except that no film-forming material was added.

[0178] <Comparative Example 6> In Example 8, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 8, except that no film-forming material was added.

[0179] <Comparative Example 7> In Example 9, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that no film-forming material was added.

[0180] <Comparative Example 8> In Example 10, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that no film-forming material was added.

[0181] <Comparative Example 9> In Example 11, a ZrO2 thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that no film-forming material was added.

[0182] 1) Vapor deposition evaluation In Examples 1 to 3, 5 to 8 and Comparative Examples 1 to 4, the inorganic precursor was changed to CpHf, in Example 4 and Comparative Example 5 the inorganic precursor was changed to TEMAHf, and in Examples 9 to 14 and Comparative Examples 6 and 7 the inorganic precursor was changed to CpZr. Overall, the deposition rate tended to decrease when the film-forming material was added before the inorganic precursor, and increase when the film-forming material was added after the inorganic precursor (see Table 1 and Figure 2 below).

[0183] As shown in Examples 1 to 6 and Comparative Examples 1 to 3, this tendency was greater at low temperatures.

[0184] Moreover, as shown in Examples 1 to 8 and Comparative Examples 1 to 3, Examples 9 to 14 and Comparative Examples 6 and 7, this tendency was more pronounced in the case of ZrO2 thin films.

[0185] [Table 1]

[0186] 2) Impurity reduction properties The carbon reduction rate (%) was calculated using the following formula 2.

[0187] [Formula 2] JPEG0007812872000013.jpg15132

[0188] As can be seen from FIG. 6 below, Examples 1 to 3, which used the film-forming material according to the present invention and an inorganic precursor as a Hf thin film precursor, showed a significant reduction in the intensity of C, a contaminant in the thin film, compared to Comparative Example 1 (Ref HfO2), which did not use a film-forming material, demonstrating excellent impurity reduction properties.

[0189] More specifically, Example 1 (corresponding to FIG. 6(a)), which used CpHf as the inorganic precursor at 320°C, showed a 76% reduction in the C intensity, a contaminant in the thin film, compared to the control, Comparative Example 1 (C(Counts / s)=8227). Example 2 (corresponding to FIG. 6(b)), which used CpHf as the inorganic precursor at 300°C, showed a 66% reduction in the C intensity, a contaminant in the thin film, compared to the control, Comparative Example 2. Example 3 (corresponding to FIG. 6(c)), which used CpHf as the inorganic precursor at 250°C, showed a 40% reduction in the C intensity, a contaminant in the thin film, compared to the control, Comparative Example 3 (C(Counts / s)=13745). These results again confirm that the Hf thin film according to the present invention has excellent impurity reduction properties.

[0190] 3) Thin film density As shown in FIG. 7, Example 2 (thin film density 9.40 g / cm 3 ), Example 3 (thin film - density 8.0 g / cm 3 ) are the results of Comparative Example 2 (9.0 g / cm 3 ) and Comparative Example 3 (7.7 g / cm 3 ), a significant increase in the film density was observed as measured based on X-ray reflectometry (XRR) analysis.

[0191] This shows that the Hf and Zr thin films according to the present invention can improve the crystallinity and ultimately the electrical characteristics in integrated structures with high aspect ratios such as DRAM capacitance.

[0192] The XRD patterns for the deposited films having a thickness of 7 nm in the above-described Examples 1 and 3 and Comparative Example 3 are shown in FIG.

[0193] As shown in Figure 9 below, an amorphous state was observed, represented by a very weak diffraction pattern, and no phase transition from 320° to a crystalline phase was observed. For reference, very thin evaporated thin films are known to be mostly amorphous, and this confirmed that a suitable thin film had been produced.

[0194] 4) Capacitance In Example 1 and Comparative Example 1, the capacitance of each of the HfO2 thin films produced was measured.

[0195] Specifically, a metal thin film was formed on the top and bottom of the dielectric film to be measured, and the metals on the top and bottom were electrically connected to each other. Measurements were then performed using a CV measurement device at a frequency of 1 MHz, and the results are shown in Table 2 below.

[0196] 5) Leakage current In Example 1 and Comparative Example 1, the leakage current of the HfO2 thin films fabricated was measured at 3 MV / cm.

[0197] Specifically, measurements were made using an IV Parameter Analyzer (Model: 4200-SCS; manufacturer: KEITHLEY) in Voltage Sweep Mode (0-15V), and the results are shown in Table 2 below.

[0198] 6) Dielectric constant In Example 1 and Comparative Example 1, the dielectric constant of each of the HfO2 thin films prepared was measured.

[0199] Specifically, measurements were carried out using a CV Parameter Analyzer (Model: E4980A, LCR Meter: 20 Hz to 2 MHz, Manufacturer: KEYSIGHT) in a DC-Bias Sweep Mode, and the results are shown in Table 2 below.

[0200] [Table 2]

[0201] As shown in Table 2, Example 1, which uses the film-forming material according to the present invention, has improved dielectric constant and capacitance, and significantly reduced leakage current, compared to Comparative Example 1, which does not use the film-forming material. Specifically, the leakage current was 5.18×10, which is lower than the limit of DRAM leakage current. -8 A / cm 2 An improvement equivalent to 95% was confirmed, and it is believed that such a large reduction in leakage current is due to the previously confirmed improvements in thin film impurities and thin film density.

[0202] 7) Bottom-up conformal properties In Example 1 and Comparative Example 1, the bottom-up conformal properties of the HfO2 thin films fabricated were confirmed.

[0203] Specifically, HfO2 thin films were deposited at 320°C on a substrate having a trench structure with an aspect ratio (length / diameter) of 22.6:1 according to Example 1 of the present invention and Comparative Example 1.

[0204] Metal thin films were formed on the top and bottom of the HfO2 thin film, and TEM images of the cross sections at 200 nm below the top and 100 nm above the bottom are shown in Figure 3 below.

[0205] As shown in FIG. 3 below, Example 1, which used the film formation material of the present invention, exhibited a top thickness of 5.17 nm and a bottom thickness of 4.99 nm, resulting in a conformal characteristic of 97% (FIG. 3b), while Comparative Example 1, which did not use the film formation material of the present invention, exhibited a top thickness of 7.98 nm and a bottom thickness of 6.96 nm, resulting in a conformal characteristic of 87% (FIG. 3a), confirming improved bottom-up conformal characteristics.

[0206] These inventive results provide strong evidence for the promising capabilities of hybrid precursor pulses in ALD to achieve excellent film quality, high film conformality, and excellent electrical performance.

[0207] The innovative approach to auxiliary precursor pulsing in the ALD process of the present invention offers various opportunities for applications such as low resistive metal gate interconnects for future technology nodes, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, and other 3D device architectures such as 3D gate-all-around (GAA) and 3D NAND.

Claims

1. A film-forming material comprising a blocking agent and a ligand exchange reactant, The blocking agent is an unsaturated hydrocarbon having 2 to 15 carbon atoms formed from the film-forming material during the film-forming process; the ligand exchange reactant is a hydrogen halide or halogen gas formed from the film-forming material during the film-forming process and undergoes an exchange reaction with the ligand of the inorganic precursor; The film-forming material is for forming a metal oxide film on a metal nitride film.

2. 2. The film-forming material according to claim 1, wherein the film-forming material is a branched, cyclic, or aromatic compound represented by the following chemical formula 1: [Chemical formula 1] AnBmXoYiZj (A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are integers from 0 to 3.)

3. A film-forming material as described in claim 1, further comprising an inorganic precursor.

4. 4. The film-forming material according to claim 3, wherein the inorganic precursor comprises one or more elements selected from the group consisting of 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.

5. The film-forming material according to claim 3, wherein the inorganic precursor is a thin film residual precursor selected from the group consisting of a compound represented by the following chemical formula 2a: a compound represented by the following chemical formula 2b: and a compound represented by the following chemical formula 2c: [Chemical formula 2a] 【Chemistry 1】 (The M １ is Zr, Hf, Si, Ge or Ti, and X １ , X ２ , X ３ is independently -NR １ R ２ OR ３ and R １ ~R ３ are independently an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2. [Chemical formula 2b] 【Chemistry 2】 (The M ２ is Zr, Hf, Si, Ge or Ti, and R １ are independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' １ , X' ２ , and X' ３ are independently -NR 1 R 2 or -OR 3 and the R 1 ~R 3 are independently an alkyl group having 1 to 6 carbon atoms. [Chemical formula 2c] 【Transformation 3】 (The M １ is Zr, Hf, Si, Ge or Ti, and X 11 and X 12 are each independently an alkyl group or -NR 3 R 4 and -OR 5 and R １ ~R ２ are each independently an alkyl group having 1 to 6 carbon atoms, １ and n ２ are each independently an integer from 0 to 5.

6. The film-forming material according to claim 3 , wherein the inorganic precursor is contained in a ratio of 1 to 99 based on the weight of the film-forming material.

7. 4. The film-forming material according to claim 3, wherein the film-forming material contains a reactive gas supplied in pulses, and the reactive gas is at least one selected from the group consisting of oxidizing agents.

8. The film-forming material according to claim 3 , wherein the film-forming material is a film-forming composition for bottom-up film formation.

9. 10. The method of claim 1, further comprising the steps of: injecting the film-forming material according to claim 1 into a chamber and depositing the material on a substrate having a metal nitride film loaded thereon; Injecting and depositing an inorganic precursor onto the substrate; and depositing a metal oxide film on the metal nitride film of the substrate by injecting a pulse of a reactive gas; The inorganic precursor is a thin film residual precursor containing at least one compound selected from the group consisting of a compound represented by the following chemical formula 2a: a compound represented by the following chemical formula 2b: and a compound represented by the following chemical formula 2c: [Chemical formula 2a] 【Chemistry 4】 (The M １ is Zr, Hf, Si, Ge or Ti, and X １ , X ２ , X ３ is independently -NR １ R ２ OR ３ and R １ ~R ３ are independently an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2. [Chemical formula 2b] 【Transformation 5】 (The M ２ is Zr, Hf, Si, Ge or Ti, and R １ are independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' １ , X' ２ , and X' ３ are independently -NR 1 R 2 or -OR 3 and the R 1 ~R 3 are independently an alkyl group having 1 to 6 carbon atoms. [Chemical formula 2c] 【Transformation 6】 (The M １ is Zr, Hf, Si, Ge or Ti, and X 11 and X 12 are each independently an alkyl group or -NR 3 R 4 and -OR 5 and R １ ~R ２ are each independently an alkyl group having 1 to 6 carbon atoms, １ and n ２ are each independently an integer from 0 to 5.

10. Injecting an inorganic precursor into the chamber and depositing it on the substrate including the loaded metal nitride film; and Injecting and depositing the film-forming material of claim 1 onto the substrate; and depositing a metal oxide film on the metal nitride film of the substrate by injecting a pulse of a reactive gas; The inorganic precursor is a thin film residual precursor containing at least one compound selected from the group consisting of a compound represented by the following chemical formula 2a: a compound represented by the following chemical formula 2b: and a compound represented by the following chemical formula 2c: [Chemical formula 2a] 【Transformation 7】 (The M １ is Zr, Hf, Si, Ge or Ti, and X １ , X ２ , X ３ is independently -NR １ R ２ OR ３ and R １ ~R ３ are independently an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2. [Chemical formula 2b] 【Transformation 8】 (The M ２ is Zr, Hf, Si, Ge or Ti, and R １ are independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' １ , X' ２ , and X' ３ are independently -NR 1 R 2 or -OR 3 and the R 1 ~R 3 are independently an alkyl group having 1 to 6 carbon atoms. [Chemical formula 2c] 【Chemistry 9】 (The M １ is Zr, Hf, Si, Ge or Ti, and X 11 and X 12 are each independently an alkyl group or -NR 3 R 4 and -OR 5 and R １ ~R ２ are each independently an alkyl group having 1 to 6 carbon atoms, １ and n ２ are each independently an integer from 0 to 5.

11. Injecting the film-forming material according to claim 1 and an inorganic precursor into a chamber and depositing the film on a substrate including a loaded metal nitride film; and depositing a metal oxide film on the metal nitride film of the substrate by injecting a pulse of a reactive gas; The inorganic precursor is a thin film residual precursor containing at least one compound selected from the group consisting of a compound represented by the following chemical formula 2a: a compound represented by the following chemical formula 2b: and a compound represented by the following chemical formula 2c: [Chemical formula 2a] 【Chemistry 10】 (The M １ is Zr, Hf, Si, Ge or Ti, and X １ , X ２ , X ３ is independently -NR １ R ２ OR ３ and R １ ~R ３ are independently an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2. [Chemical formula 2b] 【Chemistry 11】 (The M ２ is Zr, Hf, Si, Ge or Ti, and R １ are independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' １ , X' ２ , and X' ３ are independently -NR 1 R 2 or -OR 3 and the R 1 ~R 3 are independently an alkyl group having 1 to 6 carbon atoms. [Chemical formula 2c] 【Chemistry 12】 (The M １ is Zr, Hf, Si, Ge or Ti, and X 11 and X 12 are each independently an alkyl group or -NR 3 R 4 and -OR 5 and R １ ~R ２ are each independently an alkyl group having 1 to 6 carbon atoms, １ and n ２ are each independently an integer from 0 to 5.

12. The substrate has an aspect ratio of 10:1 or more. The film forming method according to claim 9.

13. 10. The film forming method according to claim 9, wherein the film forming method is performed at a temperature of 200 to 500[deg.] C.

14. The method of claim 9, wherein the film formation method is performed by atomic layer deposition, chemical vapor deposition, plasma-enhanced atomic layer deposition, or plasma-enhanced chemical vapor deposition.

15. A semiconductor thin film produced by the film formation method according to claim 9.

16. 16. The semiconductor thin film of claim 15, wherein the semiconductor thin film is a diffusion barrier film, an etch stop film, a charge trap film, a selective area deposition film, or a bottom-up thin film.

17. A semiconductor substrate comprising the semiconductor thin film according to claim 15.

18. 18. The semiconductor substrate of claim 17, wherein the semiconductor substrate is a low resistive metal gate interconnect, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D gate-all-around (GAA), or a 3D NAND.

19. A semiconductor device comprising the semiconductor substrate of claim 17.

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