Thin film processing method and method for manufacturing memory device comprising same

Abstract

According to an embodiment of the present invention, a thin film processing method comprises the steps of: supplying a capping precursor to an inside of a chamber having a substrate disposed therein to adsorb the precursor on a thin film formed on the substrate; purging the inside of the chamber; supplying a first reactive material to the inside of the chamber to form a capping layer; purging the inside of the chamber; heat-treating the substrate; supplying an etching initiator to the inside of the chamber; purging the inside of the chamber; supplying a second reactive material to the inside of the chamber to activate the etching initiator; and purging the inside of the chamber, wherein the capping precursor includes, as a central element, a metal capable of growing in the same crystal structure as that of the thin film.

Description

Thin film processing method and method for manufacturing a memory device including the same

[0001] The present invention relates to a thin film processing method and a method for manufacturing a memory device including the same, and more specifically, to a thin film processing method for improving the properties of a thin film using a capping layer and a method for manufacturing a memory device including the same.

[0002] With the advancement of integrated circuit electronic devices, improving device performance and miniaturization are becoming increasingly important challenges. In particular, in metal-oxide-semiconductor (MOS) devices, the performance of the gate dielectric significantly impacts the overall device performance. However, traditional silicon oxide (SiO2) dielectrics suffer from increased leakage current as the thickness is reduced, which reduces device reliability.

[0003]

[0004] To address this, high-k dielectric materials are being used as dielectrics. High-k dielectric materials maintain a high dielectric constant even at low thicknesses, improving electrical performance while simultaneously reducing leakage current. Therefore, high performance and reliability can be maintained even in miniaturized electronic devices.

[0005]

[0006] However, securing desired properties is difficult due to defects and impurities that arise during the process of reducing the thickness of high-k dielectric materials. Thin high-k films are more sensitive to defects and impurities, which can significantly affect overall electrical properties. Furthermore, as the thickness decreases, surface or interface effects can have a greater impact on overall physical properties. Therefore, securing high-k thin films with the desired properties while maintaining high quality is a critical technological challenge.

[0007]

[0008] Accordingly, active efforts are being made to develop high-k materials that can maintain high quality even at low thicknesses to maximize the performance and improve the reliability of semiconductor devices based on high-k metal oxides, such as low-power logic devices, non-volatile memory, and capacitors.

[0009] The purpose of the present invention is to provide a thin film processing method capable of improving the properties of a thin film using a capping layer and a method for manufacturing a memory device including the same.

[0010] Other objects of the present invention will become more apparent from the following detailed description.

[0011] According to one embodiment of the present invention, a thin film processing method includes the steps of: supplying a capping precursor into a chamber in which a substrate is placed, and adsorbing the precursor onto a thin film formed on the substrate; purging the interior of the chamber; supplying a reactant into the chamber to form a capping layer; purging the interior of the chamber; heat-treating the substrate; supplying an etching initiator into the chamber; purging the interior of the chamber; supplying a reactant into the chamber to activate the etching initiator; and purging the interior of the chamber, wherein the capping precursor has a metal that can grow into the same crystal as the thin film as a central element.

[0012] According to another embodiment of the present invention, a thin film processing method comprises the steps of forming a capping layer on a thin film formed on a substrate; heat-treating the substrate; supplying an etching initiator into a chamber in which the substrate is placed; purging the interior of the chamber; supplying a reactant into the chamber to activate the etching initiator; and purging the interior of the chamber, wherein the step of forming the capping layer comprises the steps of supplying a capping precursor into the chamber and adsorbing the capping precursor onto the thin film; purging the interior of the chamber; supplying a reactant into the chamber to form a first capping layer; purging the interior of the chamber; supplying a doping precursor into the chamber and adsorbing the doping precursor onto the thin film; purging the interior of the chamber; supplying a reactant into the chamber; And a step of purging the interior of the chamber is included, wherein the capping precursor has as a central element a metal that can grow into the same crystal as the thin film, and the doping precursor has as a central element an element that can control the coordination number of the thin film.

[0013] According to another embodiment of the present invention, a thin film processing method comprises: forming a first capping layer on a thin film formed on a substrate; forming a second capping layer on the first capping layer; heat-treating the substrate; supplying an etching initiator into a chamber in which the substrate is placed; purging the interior of the chamber; supplying a reactant into the chamber to activate the etching initiator; and purging the interior of the chamber, wherein the forming of the first capping layer comprises: supplying a first capping precursor into the chamber to adsorb the first capping precursor onto the thin film; purging the interior of the chamber; supplying a reactant into the chamber to form the first capping layer; purging the interior of the chamber; supplying a doping precursor into the chamber to adsorb the doping precursor onto the thin film; purging the interior of the chamber; supplying a reactant into the chamber; And a step of purging the inside of the chamber, wherein the step of forming the second capping layer comprises: a step of supplying a second capping precursor into the inside of the chamber to adsorb the second capping precursor onto the thin film; a step of purging the inside of the chamber; a step of supplying a reactant into the inside of the chamber to form a second capping layer; and a step of purging the inside of the chamber, wherein the first and second capping precursors have a metal capable of growing into the same crystal as the thin film as a central element, and the doping precursor has an element capable of controlling the coordination number of the thin film as a central element.

[0014] The above etching initiator can be represented by the following <Chemical Formula 1>.

[0015] <Chemical Formula 1>

[0016]

[0017] In the above <Chemical Formula 1>, n is each independently selected from an integer of 0 to 5, X1 to X3 are each independently selected from an alkoxy group having 1 to 5 carbon atoms and a dialkylamine group having 1 to 5 carbon atoms, and R is selected from hydrogen, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a dialkylamine group having 1 to 5 carbon atoms.

[0018] The above etching initiator may be any one of Trimethyl orthoformate (TMOF), Triethyl orthoformate (TEOF), Dimethylformamide dimethyl acetal (DFDA), and Tris(dimethylamino)methane (TDMAM).

[0019] The above etching initiator can be represented by the following <Chemical Formula 2> or <Chemical Formula 3>.

[0020] <Chemical Formula 2>

[0021]

[0022] <Chemical Formula 3>

[0023]

[0024] In the above <chemical formula 2> or <chemical formula 3>,

[0025] X1 and X2 may be the same or different from each other and are independently selected from hydrogen, chlorine atom, and chloroalkyl group having 1 to 5 carbon atoms,

[0026] R1 to R3 may be the same or different, and are independently selected from hydrogen, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group having 0 to 4 carbon atoms, and an alkoxy group having 0 to 4 carbon atoms.

[0027] The above etching initiator may be any one of Dichloromethyl methyl ether (DCMME), Trimethyl chloro orthoacetate (TMCOA), and Chloromethyl ethyl ether (CMEE).

[0028] The above thin film may have one of Ti, Hf, Zr, Al, and Ta as a central element.

[0029] The above capping layer may have one of Sn, Ti, Nb, Ta, Cr, Zr, Ru, Mo, Co, V, and Ru as a central element.

[0030] The above thin film may be a binary compound or a ternary compound doped with one or more elements.

[0031] The capping layer may have a cohesive energy lower than the thin film.

[0032] The capping layer may have a lower crystallization temperature than the thin film.

[0033] The above reactant may be any one of O3, O2, and H2O.

[0034] The above thin film treatment method can be performed at 50 to 700°C.

[0035] The above thin film may be any one of a metal film, a metal oxide, a metal nitride, a metal sulfide, a silicon nitride film, and a silicon oxide film.

[0036] According to one embodiment of the present invention, a method for manufacturing a memory device may include the thin film processing method described above.

[0037] According to one embodiment of the present invention, when a dielectric film is formed using a high-k material, it is difficult to form a desired crystal structure at a low thickness, so by capping the upper portion of the dielectric film with a metal oxide of a different element, the lower thin film can be induced to grow into the same crystal structure due to a similar lattice constant, thereby forming a dielectric film with a stable crystal structure.

[0038]

[0039] At this time, since the capping metal oxide layer has a lower crystallization temperature than the underlying thin film, the temperature at which the underlying thin film crystallizes into the target crystal can be lowered, which can improve the surface roughness of the underlying thin film. Furthermore, the capping layer is expected to reduce interfacial crystal mismatch, resulting in smoother growth of the surface of the underlying thin film and improved surface roughness.

[0040]

[0041] In this case, some of the capping layer remains, and the thickness of the capping layer is limited to prevent degradation of properties due to this. Therefore, it is difficult to form a capping layer of sufficient thickness to obtain a dielectric film of a desired crystal structure. However, according to the present invention, since the capping layer can be removed through an ALE process after capping the dielectric film, it is possible to form a capping layer of sufficient thickness to obtain a dielectric film of a desired crystal structure. In this process, in order to selectively etch only the capping layer without deteriorating the properties of the dielectric film, the capping layer can be uniformly removed through an atomic layer etching process that controls the etching degree with self-limiting etching characteristics.

[0042]

[0043] According to the invention, even if a capped film on a dielectric film crystallizes, the capping layer can be removed through a subsequent ALE process, thereby enabling the formation of a capping layer of sufficient thickness to obtain a dielectric film with a desired crystal structure. In this case, the capping layer must be made of a material that is easier to etch than the underlying film in the crystal structure.

[0044] Figure 1 is a drawing showing the etching result after heat treatment for a thin film formed on top, which is a metal oxide film.

[0045] Figure 2 is a drawing showing the etching results after heat treatment for a thin film formed on top, which is a doped metal oxide film.

[0046] Figure 3 is a drawing showing the etching results after heat treatment for a thin film having a metal oxide film and a doped metal oxide film formed on top.

[0047] Figure 4 is a flowchart showing a thin film processing method according to an embodiment of the present invention.

[0048] Figure 5 is a graph schematically showing a supply cycle according to an embodiment of the present invention.

[0049] Figure 6 is a table showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 1 / Example 1 of the present invention.

[0050] Figure 7 is a graph showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 1 / Example 1 of the present invention.

[0051] Figure 8 is a flowchart showing a thin film processing method according to another embodiment of the present invention.

[0052] Figure 9 is a graph schematically showing a supply cycle according to another embodiment of the present invention.

[0053] Figure 10 is a flowchart showing a thin film processing method according to another embodiment of the present invention.

[0054] Figure 11 is a table showing the analysis results by XRD (X-ray Diffraction) for Comparative Example 2 / Example 2 of the present invention.

[0055] Figure 12 is a graph showing the analysis results by XRD (X-ray Diffraction) for Comparative Example 2 / Example 2 of the present invention.

[0056] Figure 13 is a table showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 3 / Example 3 of the present invention.

[0057] Figure 14 is a graph showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 3 / Example 3 of the present invention.

[0058] Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the attached Figures 1 to 14. The embodiments of the present invention may be modified in various ways, and the scope of the present invention should not be construed as being limited to the embodiments described below. These embodiments are provided to explain the present invention in more detail to those skilled in the art. Accordingly, the shapes of each element shown in the drawings may be exaggerated to emphasize a clearer description.

[0059]

[0060] Figure 1 is a drawing showing the etching results after heat treatment for a thin film formed on top, which is a metal oxide film. Figure 2 is a drawing showing the etching results after heat treatment for a thin film formed on top, which is a doped metal oxide film. Figure 3 is a drawing showing the etching results after heat treatment for a thin film formed on top, which is a metal oxide film and a doped metal oxide film.

[0061]

[0062] The capping layer (or capping layer) is a material with lower cohesive energy than the underlying thin film, so it can be easily etched because the energy required for atoms in the solid state to be broken down into individual atoms is low (see Fig. 1). In addition, by doping with an element that can lower the coordination number of the capping layer, the central element of the capping layer is more exposed to the surface, increasing the reactivity, so it can be easily etched in the subsequent ALE process (see Fig. 2). In this case, by depositing a second capping layer on top of the doped capping layer that can assist in the crystallization of the doped capping layer, it can help improve the crystallinity of the underlying thin film of the doped capping layer, thereby significantly improving the crystallinity of the underlying thin film (see Fig. 3).

[0063]

[0064] The above-described method provides a low-thickness dielectric layer with improved stability and a high permittivity. Such a thin-film structure can be used in various electronic devices such as transistors, capacitors, and integrated circuit elements, and can improve the characteristics of such electronic devices.

[0065]

[0066] Fig. 4 is a flowchart showing a thin film processing method according to an embodiment of the present invention, and Fig. 5 is a graph schematically showing a supply cycle according to an embodiment of the present invention. A substrate is loaded into a process chamber, and the substrate has a thin film formed on its surface. The thin film may have one of Ti, Hf, Zr, Al, and Ta as a central element, and the thin film may be any one of a metal film, a metal oxide, a metal nitride, a metal sulfide, a silicon nitride film, and a silicon oxide film. The thin film may be a binary compound or a ternary compound doped with one or more elements.

[0067]

[0068] Meanwhile, the following process conditions can be adjusted. The process conditions may include the temperature of the substrate or process chamber, chamber pressure, and gas flow rate, and the temperature is 50 to 700°C.

[0069]

[0070] The substrate is exposed to a capping precursor supplied inside the chamber, and the precursor is adsorbed onto a thin film formed on the substrate. The capping precursor may have one of Sn, Ti, Nb, Ta, Cr, Zr, Ru, Mo, and Co as its central element.

[0071]

[0072] Afterwards, a purge gas (e.g., an inert gas such as Ar) is supplied inside the chamber to remove or purify any unabsorbed precursor or byproduct.

[0073]

[0074] Thereafter, the substrate is exposed to a reactant (or reactive gas) supplied inside the chamber, and a capping layer is formed by the reactant. The reactant can be any one of O3, O2, H2O, NH3, and H2. The capping layer has one of Sn, Ti, Nb, Ta, Cr, Zr, Ru, Mo, and Co as its central element, and the capping layer has lower cohesive energy and lower crystallization temperature than the thin film.

[0075]

[0076] Afterwards, a purge gas (e.g., an inert gas such as Ar) is supplied to the inside of the chamber to remove or purify unreacted substances or byproducts.

[0077]

[0078] Afterwards, heat treatment (annealing) is performed on the substrate, and the heat treatment can be performed at 50 to 700°C, specifically 500°C, in an O2 atmosphere.

[0079]

[0080] Thereafter, the substrate is exposed to an etching initiator supplied inside the chamber. The etching initiator can be represented by the following <Chemical Formula 1>.

[0081] <Chemical Formula 1>

[0082]

[0083] In the above <Chemical Formula 1>, n is each independently selected from an integer of 0 to 5, X1 to X3 are each independently selected from an alkoxy group having 1 to 5 carbon atoms and a dialkylamine group having 1 to 5 carbon atoms, and R is selected from hydrogen, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a dialkylamine group having 1 to 5 carbon atoms.

[0084]

[0085] Specifically, the etching initiator may be any one of Trimethyl orthoformate (TMOF), Triethyl orthoformate (TEOF), Dimethylformamide dimethyl acetal (DFDA), and Tris(dimethylamino)methane (TDMAM).

[0086]

[0087] Additionally, the etching initiator may be represented by <Chemical Formula 2> or <Chemical Formula 3>.

[0088] <Chemical Formula 2>

[0089]

[0090] <Chemical Formula 3>

[0091]

[0092] In the above <chemical formula 2> or <chemical formula 3>,

[0093] X1 and X2 may be the same or different from each other and are independently selected from hydrogen, chlorine atom, and chloroalkyl group having 1 to 5 carbon atoms,

[0094] R1 to R3 may be the same or different, and are independently selected from hydrogen, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group having 0 to 4 carbon atoms, and an alkoxy group having 0 to 4 carbon atoms.

[0095]

[0096] Specifically, the etching initiator may be any one of Dichloromethyl methyl ether (DCMME), Trimethyl chloro orthoacetate (TMCOA), and Chloromethyl ethyl ether (CMEE).

[0097]

[0098] Afterwards, a purge gas (e.g., an inert gas such as Ar) is supplied to the inside of the chamber to remove or purify any unabsorbed etching initiator or byproducts.

[0099]

[0100] Thereafter, the substrate is exposed to a reactive substance (or reactive gas) supplied inside the chamber, and etching is activated by the reactive substance. The reactive substance may be any one of O3, O2, H2O, NH3, and H2.

[0101]

[0102] Afterwards, a purge gas (e.g., an inert gas such as Ar) is supplied to the inside of the chamber to remove or purify unreacted substances or byproducts.

[0103]

[0104] FIG. 6 is a table showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 1 / Example 1 of the present invention, and FIG. 7 is a graph showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 1 / Example 1 of the present invention.

[0105]

[0106] - Comparative Example 1

[0107] 1) A TiO2 thin film with a thickness of 50 Å was prepared by depositing it on a TiN / SiO substrate through an ALD process.

[0108] 2) Deposit 20 Å of SnO2 on the thin film to form a capping layer on top of TiO2.

[0109] 3) Heat treatment was performed for 10 minutes at a process temperature of 400℃ in an O2 atmosphere.

[0110]

[0111] As a result of analysis using XRF (X-ray fluorescence spectrometry), the Ti content was confirmed to be 0.3197 and the Sn content was confirmed to be 0.0860.

[0112]

[0113] - Example 1

[0114] 1) A TiO2 thin film with a thickness of 50 Å was prepared by depositing it on a TiN / SiO substrate through an ALD process.

[0115] 2) Deposit 20 Å of SnO2 on the thin film to form a capping layer on top of TiO2.

[0116] 3) Heat treatment was performed for 10 minutes at a process temperature of 400℃ in an O2 atmosphere.

[0117] 4) Chloromethyl ethyl ether (CMEE), an etching initiator, is adsorbed at 340°C, and then O3 is supplied as a reactant (or reactive gas) to activate etching and remove the capping layer, SnO2.

[0118]

[0119] As a result of analysis using XRF (X-ray fluorescence spectrometry), the Ti content was confirmed to be 0.3128 and the Sn content was confirmed to be 0.0056.

[0120]

[0121] That is, when ALE was performed after depositing and heat-treating a SnO2 capping layer on TiO2, it was confirmed that more than 90% of SnO2 was removed, but TiO2 was not removed.

[0122]

[0123] FIG. 8 is a flowchart showing a thin film processing method according to another embodiment of the present invention, and FIG. 9 is a graph schematically showing a supply cycle according to another embodiment of the present invention.

[0124]

[0125] Unlike the previously described examples, when doping with an element capable of lowering the coordination number of the capping layer in FIGS. 8 and 9, the central element of the capping layer is more exposed to the surface, increasing reactivity, so etching can be facilitated in the subsequent ALE process.

[0126]

[0127] Figure 10 is a flowchart showing a thin film processing method according to another embodiment of the present invention.

[0128]

[0129] When a second capping layer that can help crystallize the doped capping layer is deposited on top of the doped capping layer, it can have the effect of improving the crystallinity of the lower thin film of the doped capping layer, and as a result, can have the effect of significantly improving the crystallinity of the lower thin film.

[0130]

[0131] When using a doped capping layer as shown in FIGS. 8 to 10, the etching speed of the capping layer can be improved, maximizing the effect of selectively etching only the capping layer without affecting the underlying film. This facilitates control of the capping film thickness, maximizing process reproducibility and preventing yield reduction due to process variations during device manufacturing. Furthermore, process reliability can be enhanced by uniformly etching only the capping film through a self-limiting reaction even in complex three-dimensional structures such as high aspect ratio structures.

[0132]

[0133] Fig. 11 is a table showing the analysis results by XRD (X-ray Diffraction) for Comparative Example 2 / Example 2 of the present invention, and Fig. 12 is a graph showing the analysis results by XRD (X-ray Diffraction) for Comparative Example 2 / Example 2 of the present invention.

[0134]

[0135] - Comparative Example 2

[0136] 1) Prepare a TiO2 thin film with a thickness of 50 Å deposited on a Si substrate through an ALD process.

[0137] 2) Heat treatment was performed for 10 minutes at a process temperature of 500℃ in an O2 atmosphere.

[0138]

[0139] *

[0140] XRD analysis of the above thin film confirmed Anatase-TiO2Peak.

[0141]

[0142] - Example 2

[0143] 1) Prepare a TiO2 thin film with a thickness of 50 Å deposited on a Si substrate through an ALD process.

[0144] 2) Deposit 50 Å of SnO2 on the thin film to form a capping layer on top of TiO2.

[0145] 3) Heat treatment was performed for 10 minutes at a process temperature of 500℃ in an O2 atmosphere.

[0146]

[0147] As a result of XRD analysis of the above thin film, it was confirmed that the peak moved to the Rutile-SnO2(110) and Rutile-TiO2(110) peak positions. Consequently, it was confirmed that the crystallinity of the TiO2 peak can be controlled when SnO2 is capped on top of TiO2 and then heat treatment is performed.

[0148]

[0149] Fig. 13 is a table showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 3 / Example 3 of the present invention, and Fig. 14 is a graph showing the analysis results by XRF (X-ray fluorescence spectrometry) for Comparative Example 3 / Example 3 of the present invention.

[0150]

[0151] - Comparative Example 3

[0152] 1) Prepare a TiO2 thin film with a thickness of 50 Å deposited on a Si substrate through an ALD process.

[0153] 2) Heat treatment was performed for 30 minutes at a process temperature of 500℃ in an O2 atmosphere.

[0154]

[0155] As a result of analysis by XRF (X-ray fluorescence spectrometry), the Ti content was confirmed to be 0.43408 and the Sn content was confirmed to be 1.33866.

[0156]

[0157] - Example 3

[0158] 1) Prepare a TiO2 thin film with a thickness of 50 Å deposited on a Si substrate through an ALD process.

[0159] 2) Heat treatment was performed for 30 minutes at a process temperature of 500℃ in an O2 atmosphere.

[0160] 3) Chloromethyl ethyl ether (CMEE), an etching initiator, is adsorbed at 340°C, and then O3 is supplied as a reactant (or reactive gas) to activate etching and remove the capping layer, SnO2.

[0161]

[0162] As a result of analysis using XRF (X-ray fluorescence spectrometry), the Ti content was confirmed to be 0.41969 and the Sn content was confirmed to be 0.21139.

[0163]

[0164] As a result, it was confirmed that Sn was reduced by 84%, while Ti was barely reduced by 3%. Consequently, it was confirmed that when SnO2 was capped on TiO2 and then removed through ALE, the crystallized SnO2 capping film could be selectively removed.

[0165]

[0166] As a result of the above-described embodiment, after the capping layer controls the crystallization characteristics of the dielectric film (e.g., TiO2), the capping layer can be selectively removed using an etching initiator (e.g., CMEE) and an etching activator (e.g., O3), thereby preventing degradation of characteristics due to the remaining capping layer. In this case, a dielectric film having a desired crystal structure (e.g., Rutile TiO2) with a high permittivity can be formed with a low thickness, and thus can be used in various electronic devices such as transistors, capacitors, and integrated circuit devices to improve the characteristics of the electronic devices.

[0167]

[0168] Examples showing the results of each step can be combined and used together, for example, after depositing a capping layer on a target thin film whose crystallinity is to be controlled, heat treatment is performed (for example, the heat treatment temperature can be performed at 50 to ~700°C) to secure the desired crystallinity, and then the capping layer can be selectively etched using an etching initiator (for example, the etching initiator can be any one of <Chemical Formula 1> to <Chemical Formula 3>) and an etching activator (for example, the etching activator can be any one of O3, O2, H2O, NH3, H2, which are reactants).

[0169]

[0170] At this time, since the capping layer crystallizes at a lower temperature than the target thin film, not only can the crystallization temperature of the target thin film be lowered, but also the crystal mismatch at the interface can be reduced, which can be expected to have the effect of improving the surface roughness of the target thin film. This roughness improvement effect can have the effect of improving electrical characteristics, etc. in semiconductor devices. For example, if the surface roughness of the dielectric film is large, the leakage current at the electrode and dielectric interface can increase, which can reduce device reliability and yield.

[0171]

[0172] In addition, since the capping layer can be removed, a capping layer of sufficient thickness can be formed to obtain a dielectric film of the desired crystal structure.

[0173]

[0174] While the present invention has been described in detail above through examples, other embodiments are possible. Therefore, the technical spirit and scope of the claims set forth below are not limited to the examples.

[0175] The present invention can be applied to various types of semiconductor manufacturing methods.

Claims

1. A step of supplying a capping precursor into the interior of a chamber where a substrate is placed and adsorbing the precursor onto a thin film formed on the substrate; A step of purging the interior of the chamber; A step of supplying a reactant into the interior of the chamber to form a capping layer; A step of purging the interior of the chamber; A step of heat treating the above substrate; A step of supplying an etching initiator into the interior of the chamber; A step of purging the interior of the chamber; A step of activating the etching initiator by supplying a reactive material into the interior of the chamber; and Including a step of purging the interior of the chamber, A thin film processing method in which the capping precursor comprises a metal that can grow into the same crystal as the thin film as a central element.

2. A step of forming a capping layer on a thin film formed on a substrate; A step of heat treating the above substrate; A step of supplying an etching initiator into the interior of a chamber in which the substrate is placed; A step of purging the interior of the chamber; A step of activating the etching initiator by supplying a reactive material into the interior of the chamber; and Including a step of purging the interior of the chamber, The step of forming the capping layer is: A step of supplying a capping precursor into the interior of the chamber and adsorbing the capping precursor onto the thin film; A step of purging the interior of the chamber; A step of forming a first capping layer by supplying a reactant into the interior of the chamber; A step of purging the interior of the chamber; A step of supplying a doping precursor into the interior of the chamber and adsorbing the doping precursor onto the thin film; A step of purging the interior of the chamber; A step of supplying a reaction material into the interior of the chamber; and Including a step of purging the interior of the chamber, The above capping precursor has a metal as a central element that can grow into the same crystal as the above thin film, A thin film processing method in which the above doping precursor has as its central element an element capable of controlling the coordination number of the thin film.

3. A step of forming a first capping layer on a thin film formed on a substrate; A step of forming a second capping layer on the first capping layer; A step of heat treating the above substrate; A step of supplying an etching initiator into the interior of a chamber in which the substrate is placed; A step of purging the interior of the chamber; A step of activating the etching initiator by supplying a reactive material into the interior of the chamber; and Including a step of purging the interior of the chamber, The step of forming the first capping layer is: A step of supplying a first capping precursor into the interior of the chamber and adsorbing the first capping precursor onto the thin film; A step of purging the interior of the chamber; A step of forming a first capping layer by supplying a reactant into the interior of the chamber; A step of purging the interior of the chamber; A step of supplying a doping precursor into the interior of the chamber and adsorbing the doping precursor onto the thin film; A step of purging the interior of the chamber; A step of supplying a reaction material into the interior of the chamber; and A step of purging the interior of the chamber is included, The step of forming the second capping layer is: A step of supplying a second capping precursor into the interior of the chamber and adsorbing the second capping precursor onto the thin film; A step of purging the interior of the chamber; A step of forming a second capping layer by supplying a reactant into the interior of the chamber; and Including a step of purging the interior of the chamber, The above first and second capping precursors have a metal as a central element that can grow into the same crystal as the above thin film, A thin film processing method in which the above doping precursor has as its central element an element capable of controlling the coordination number of the thin film.

4. In any one of paragraphs 1 to 3, A thin film processing method, wherein the etching initiator is represented by the following <Chemical Formula 1>. <Chemical Formula 1> In the above <Chemical Formula 1>, n is each independently selected from an integer of 0 to 5, X1 to X3 are each independently selected from an alkoxy group having 1 to 5 carbon atoms and a dialkylamine group having 1 to 5 carbon atoms, and R is selected from hydrogen, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a dialkylamine group having 1 to 5 carbon atoms.

5. In paragraph 4, A method for treating a thin film, wherein the etching initiator is any one of Trimethyl orthoformate (TMOF), Triethyl orthoformate (TEOF), Dimethylformamide dimethyl acetal (DFDA), and Tris(dimethylamino)methane (TDMAM).

6. In any one of paragraphs 1 to 3, A method for forming a thin film, wherein the etching initiator is represented by the following <Chemical Formula 2> or <Chemical Formula 3>. <Chemical Formula 2> <Chemical Formula 3> In the above <chemical formula 2> or <chemical formula 3>, X1 and X2 may be the same or different from each other and are independently selected from hydrogen, chlorine atom, and chloroalkyl group having 1 to 5 carbon atoms, R1 to R3 may be the same or different, and are independently selected from hydrogen, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group having 0 to 4 carbon atoms, and an alkoxy group having 0 to 4 carbon atoms.

7. In paragraph 6, A method for treating a thin film, wherein the etching initiator is any one of Dichloromethyl methyl ether (DCMME), Trimethyl chloro orthoacetate (TMCOA), and Chloromethyl ethyl ether (CMEE).

8. In any one of paragraphs 1 to 3, A method for processing a thin film, wherein the above thin film is a metal oxide thin film having one of Ti, Hf, Zr, Al, and Ta as a central element.

9. In any one of paragraphs 1 to 3, A thin film processing method, wherein the capping layer is a metal oxide thin film having one of Sn, Ti, Nb, Ta, Cr, Zr, Ru, Mo, Co, V, and Ru as a central element.

10. In any one of paragraphs 1 to 3, A method for processing a thin film, wherein the thin film is a binary compound or ternary compound doped with one or more elements.

11. In any one of paragraphs 1 to 3, A thin film processing method wherein the capping layer has a cohesive energy lower than that of the thin film.

12. In any one of paragraphs 1 to 3, A thin film processing method wherein the capping layer has a lower crystallization temperature than the thin film.

13. In any one of paragraphs 1 to 3, A thin film processing method wherein the above reactant is any one of O3, O2, and H2O.

14. In any one of paragraphs 1 to 3, The above thin film treatment method is a thin film treatment method that is performed at 50 to 700°C.

15. In any one of paragraphs 1 to 3, A method for processing a thin film, wherein the thin film is any one of a metal film, a metal oxide, a metal nitride, a metal sulfide, a silicon nitride film, and a silicon oxide film.

16. A method for manufacturing a memory device, comprising the thin film processing method described in any one of claims 1 to 3.

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