Method of treating thin films and method of manufacturing memory device, comprising same

Abstract

A method of treating thin films, according to one embodiment of the present invention, comprises the steps of: treating a substrate by supplying a surface oxidant into a chamber in which the substrate is placed; supplying a precursor into the chamber and adsorbing the precursor onto the substrate; purging the inside of the chamber; supplying an etch initiator into the chamber; purging the inside of the chamber; forming a thin film by supplying a reactant into the chamber, and activating the etch initiator; and purging the inside of the chamber.

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 through oxidation treatment of a substrate surface and a method for manufacturing a memory device including the same.

[0002] The main mechanism of conventional top-down patterning has been to deposit the desired material in the form of a thin film and then fabricate it into the desired size and shape through isotropic wet etching, anisotropic dry etching, reactive ion etching (RIE). However, due to the continuous demand for high performance and low power, along with the increasingly ultra-fine pattern size, there is a need for innovation beyond the current three-dimensional and multi-dimensional layered structure, and an etching technology with high precision at the atomic level, such as atomic layer etching (ALE), is required beyond the existing wet / dry etching technology.

[0003]

[0004] Hydrogen fluoride, used in conventional atomic layer etching, possesses strong reactivity and offers excellent etching performance. However, its rapid reaction rate makes it difficult to etch very thin layers. Furthermore, fluorine atoms can penetrate undesirable areas during the surface removal process, potentially degrading device characteristics.

[0005]

[0006] Therefore, a halide-free etching material and process that are less reactive than hydrogen fluoride and do not deteriorate the characteristics of the device when left behind were introduced. However, due to the characteristics of the halide-free etching material, the etching speed is low due to its lower reactivity than hydrogen fluoride, making it difficult to precisely control the etching degree.

[0007]

[0008] Meanwhile, to overcome the limitations of etching materials with low reactivity, a selective adsorption process that utilizes the characteristic that the degree of decomposition of the precursor varies depending on the reactivity of the substrate surface and the precursor was applied to the pre-etching stage to significantly improve selectivity, but there are still concerns about deterioration of properties due to some metal remaining in the non-growth region.

[0009] The purpose of the present invention is to provide a method for forming a thin film capable of maximizing selectivity 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 surface oxidizer into a chamber in which a substrate is placed, thereby processing the substrate; supplying a precursor into the chamber, thereby adsorbing the precursor onto the substrate; purging the interior of the chamber; supplying an etching initiator into the chamber; purging the interior of the chamber; supplying a reactant into the chamber to form a thin film and activate the etching initiator; and purging the interior of the chamber.

[0012] According to another embodiment of the present invention, a thin film processing method includes the steps of: supplying a surface oxidizer into a chamber in which a substrate is placed, thereby processing a thin film formed on the substrate; supplying a precursor into the chamber, thereby adsorbing the precursor onto the substrate; purging the interior of the chamber; supplying an accelerating substance into the chamber; purging the interior of the chamber; supplying an etching initiator into the chamber; purging the interior of the chamber; supplying a reactant into the chamber to form a thin film and activate the etching initiator; and purging the interior of the chamber.

[0013] According to another embodiment of the present invention, a thin film processing method includes the steps of: supplying a surface oxidizing agent into a chamber in which a substrate is placed, thereby processing the substrate; supplying a precursor into the chamber, thereby adsorbing the precursor onto the substrate; purging the interior of the chamber; supplying a first etching initiator into the chamber; purging the interior of the chamber; supplying an accelerating material into the chamber; purging the interior of the chamber; supplying a second etching initiator into the chamber; purging the interior of the chamber; supplying a reactant into the chamber to form a thin film and activate the etching initiator; and purging the interior of the chamber.

[0014] The above surface oxidizer may be any one of O3, O2, and H2O.

[0015] The above etching initiator can be represented by the following <Chemical Formula 1>.

[0016] <Chemical Formula 1>

[0017]

[0018] 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.

[0019] The above etching initiator may be any one of Trimethyl orthoformate (TMOF), Triethyl orthoformate (TEOF), Dimethylformamide dimethyl acetal (DFDA), and Tris(dimethylamino)methane.

[0020] The above etching initiator can be represented by the following <Chemical Formula 2> or the following <Chemical Formula 3>.

[0021] <Chemical Formula 2>

[0022]

[0023] <Chemical Formula 3>

[0024]

[0025] In the above <chemical formula 2> or <chemical formula 3>,

[0026] X1 to 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,

[0027] 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, an alkoxy group having 0 to 4 carbon atoms, and a dialkylamine group having 0 to 4 carbon atoms.

[0028] The above etching initiator may be any one of dichloromethyl methyl ether (DCMME) and 1-chloromethyl ethyl ether (1-CMEE).

[0029] The above precursor may have one of Al, Ti, Hf, Nb, Ta, Mo, W, Zr, Ru, Sn, and Cr as a central element.

[0030] The above thin film may be any one of a metal film, a metal oxide, a metal nitride, a metal sulfide, silicon nitride, and silicon oxide.

[0031] The above thin film may be a binary compound or a ternary compound doped with one or more elements.

[0032] The above thin film treatment method can be performed at 50 to 700°C.

[0033] According to one embodiment of the present invention, a method for manufacturing a memory device may include the thin film processing method described above.

[0034] According to one embodiment of the present invention, by oxidation treatment of the substrate surface, surface reactivity is increased in a growth region to promote decomposition and / or adsorption of a precursor, and in a non-growth region, the composition of the etching surface is changed to lower surface energy, thereby promoting the precursor desorption effect of the etchant, and consequently, selectivity can be maximized by improving the etching performance of metal remaining in the non-growth region.

[0035] Figure 1 is a flowchart showing a thin film processing method according to one embodiment of the present invention.

[0036] Figure 2 is a graph schematically showing a supply cycle according to one embodiment of the present invention.

[0037] Figure 3 is a flowchart showing a thin film processing method according to another embodiment of the present invention.

[0038] Figure 4 is a graph schematically showing a supply cycle according to another embodiment of the present invention.

[0039] Figure 5 is a table showing the niobium content and selectivity according to Comparative Example 1 and Example 1 of the present invention.

[0040] Figures 6 and 7 are graphs showing the niobium content according to Figure 5.

[0041] Figure 8 is a table showing the niobium content and selectivity according to Comparative Example 2 and Example 2 of the present invention.

[0042] Figures 9 and 10 are graphs showing the niobium content according to Figure 8.

[0043] Figure 11 is a table showing the niobium content and selectivity according to Comparative Example 3 and Example 3 of the present invention.

[0044] Figures 12 and 13 are graphs showing the niobium content according to Figure 11.

[0045] Figures 14 and 15 are graphs showing changes in the content and selectivity of niobium in the non-growth region depending on whether or not O3 surface treatment is performed.

[0046] Figure 16 is a table showing the niobium content and selectivity according to Comparative Example 4 and Example 4 of the present invention.

[0047] Figure 17 is a graph showing the niobium content according to Example 4 of the present invention.

[0048] Figure 18 is a table showing the tantalum content and selectivity according to Comparative Example 5 and Example 5 of the present invention.

[0049] Figure 19 is a graph showing the tantalum content according to Example 5 of the present invention.

[0050] Figure 20 is a flowchart showing a thin film processing method according to another embodiment of the present invention.

[0051] Figure 21 is a graph schematically showing a supply cycle according to another embodiment of the present invention.

[0052] Figure 22 is a table showing the niobium content and selectivity according to Comparative Example 6 and Example 6 of the present invention.

[0053] Figure 23 is a graph showing the niobium content according to Example 6 of the present invention.

[0054] Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the attached Figures 1 to 23. 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.

[0055]

[0056] FIG. 1 is a flowchart illustrating a thin film processing method according to one embodiment of the present invention, and FIG. 2 is a graph schematically illustrating a supply cycle according to one embodiment of the present invention. A substrate is loaded into a process chamber, and 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.

[0057]

[0058] The substrate is exposed to a surface oxidizer (or surface treatment agent) supplied inside the chamber, and the substrate is treated by the surface oxidizer. The surface oxidizer may be any one of O3, O2, and H2O. The above process corresponds to the first process illustrated in FIGS. 1 and 2.

[0059]

[0060] Thereafter, the substrate is exposed to a precursor supplied inside the chamber, and the precursor is adsorbed onto the substrate. The precursor may have one of Al, Ti, Hf, Nb, Ta, Mo, W, Zr, Ru, Sn, or Cr as its central element. At this time, the precursor supply step is performed at 50 to 700°C.

[0061]

[0062] 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.

[0063]

[0064] The above process corresponds to the second process illustrated in FIGS. 1 and 2, and the following process corresponds to the third process illustrated in FIGS. 1 and 2. The thin film is processed through the following process.

[0065]

[0066] The substrate is exposed to an etching initiator supplied inside the chamber. The etching initiator supply step is performed at a temperature of 50 to 700°C. The etching initiator can be represented by the following <Chemical Formula 1>.

[0067] <Chemical Formula 1>

[0068]

[0069] 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.

[0070]

[0071] Specifically, the etching initiator may be any one of Trimethyl orthoformate (TMOF), Triethyl orthoformate (TEOF), Dimethylformamide dimethyl acetal (DFDA), and Tris(dimethylamino)methane.

[0072]

[0073] Additionally, the etching initiator may be represented by the following <Chemical Formula 2> or the following <Chemical Formula 3>.

[0074] <Chemical Formula 2>

[0075]

[0076] <Chemical Formula 3>

[0077]

[0078] In the above <chemical formula 2> or <chemical formula 3>,

[0079] X1 to 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,

[0080] 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, an alkoxy group having 0 to 4 carbon atoms, and a dialkylamine group having 0 to 4 carbon atoms.

[0081]

[0082] Specifically, the etching initiator may be any one of Dichloromethyl methyl ether (DCMME) and 1-chloromethyl ethyl ether (1-CMEE).

[0083]

[0084] 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.

[0085]

[0086] Thereafter, the substrate is exposed to a reactant supplied inside the chamber, and etching is activated while a thin film is formed by the reactant. The reactant may be any one of O3, O2, H2O, NH3, and H2.

[0087]

[0088] *

[0089] 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.

[0090]

[0091] Fig. 3 is a flowchart illustrating a thin film processing method according to another embodiment of the present invention, and Fig. 4 is a graph schematically illustrating a supply cycle according to another embodiment of the present invention. Unlike the previous embodiment, after a precursor is adsorbed onto a thin film formed on a substrate, unadsorbed precursor or byproducts are removed through a purge gas, the substrate is exposed to a promoting substance supplied inside the chamber, and the adsorption of the precursor onto the substrate is promoted by the promoting substance. Preferably, the promoting substance is O2, but may be replaced with O3 or H2O.

[0092]

[0093] Meanwhile, when promoting adsorption through a promoter is specifically explained, unlike when metal oxides are formed when O3 is supplied under the same process conditions, when O2 is supplied, the oxidation reaction progresses slowly, forming metal oxides with relatively weak bonds, which plays a role in assisting the surface dependent adsorption (SDA) process.

[0094]

[0095] 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.

[0096]

[0097] - Comparative Example 1 - SDA (surface dependent adsorption) + ALE (atomic layer etch)

[0098]

[0099] Unlike Example 1 described below, the surface treatment process corresponding to the first process was not performed.

[0100]

[0101] In the second process, niobium precursor was adsorbed on the SiCN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through the SDA process, respectively. The process temperature was 340 ℃, and no reactants were used.

[0102]

[0103] The third process supplied Trimethyl Orthoformate as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0104]

[0105] The process of supplying niobium precursor and etching initiator is as follows, and processes 1)-2) below were carried out as the second process, and processes 3)-6) were carried out as the third process.

[0106]

[0107] 1) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0108] 2) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0109] 3) Using Ar as a carrier gas, the etching initiator Trimethyl Orthoformate is supplied to the reaction chamber and adsorbed on the SiCN substrate and TiN substrate.

[0110] 4) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0111] 5) Supply O3 gas to the reaction chamber to activate etching.

[0112] 6) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0113]

[0114] When the second process was repeated 100 times and the third process was repeated 100 times, the niobium content was confirmed to be 0.75% (TiN substrate) and 0.19% (SiCN substrate), and the selectivity was confirmed to be 3.9:1 (see Figs. 5 and 6).

[0115]

[0116] - Example 1 - Surface oxidation treatment + SDA (surface dependent adsorption) + ALE (atomic layer etch)

[0117]

[0118] The first process activated the surfaces of the SiCN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through an O3 surface treatment process. The process temperature was 340°C and lasted for 10 minutes.

[0119]

[0120] In the second process, niobium precursor was adsorbed on SiCN substrate and TiN substrate through SDA process, respectively. The process temperature was 340 ℃, and no reactants were used.

[0121]

[0122] The third process supplied Trimethyl Orthoformate as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0123]

[0124] The process of supplying niobium precursor and etching initiator is as follows, and process 1) below is the first process, processes 2)-3) are the second process, and processes 4)-7) are the third process (see Figures 1 and 2).

[0125]

[0126] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiCN substrate and TiN substrate.

[0127] 2) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0128] 3) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0129] 4) Using Ar as a carrier gas, the etching initiator Trimethyl Orthoformate is supplied to the reaction chamber and adsorbed on the SiCN substrate and TiN substrate.

[0130] 5) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0131] 6) Supply O3 gas to the reaction chamber to activate etching.

[0132] 7) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0133]

[0134] After the first process was performed for 10 minutes, the second process was repeated 100 times, and the third process was repeated 100 times, the niobium content was confirmed to be 0.89% (TiN substrate) and 0.11% (SiCN substrate), and the niobium in the non-growth region was confirmed to be reduced by approximately 42% compared to Comparative Example 1, resulting in a selectivity of 8.1:1 (see FIGS. 5 and 7).

[0135]

[0136] In conclusion, when the O3 surface treatment process was applied, the selective etching effect of the non-metallic thin film SiCN substrate on the metal thin film TiN substrate was enhanced.

[0137]

[0138] - Comparative Example 2 - SDA (surface dependent adsorption) + ALE (atomic layer etch)

[0139]

[0140] Unlike Example 2 described below, the surface treatment process corresponding to the first process was not performed.

[0141]

[0142] In the second process, niobium precursor was adsorbed on the SiCN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through the SDA process, respectively. The process temperature was 220 ℃, and no reactants were used.

[0143]

[0144] The third process supplied Trimethyl Orthoformate as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0145]

[0146] The process of supplying niobium precursor and etching initiator is as follows, and processes 1)-2) below were carried out as the second process, and processes 3)-6) were carried out as the third process.

[0147]

[0148] 1) Using Ar as a carrier gas, the niobium precursor TBTEMNb is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0149] 2) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0150] 3) Using Ar as a carrier gas, the etching initiator Trimethyl Orthoformate is supplied to the reaction chamber and adsorbed on the SiCN substrate and TiN substrate.

[0151] 4) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0152] 5) Supply O3 gas to the reaction chamber to activate etching.

[0153] 6) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0154]

[0155] When the second process was repeated 100 times and the third process was repeated 100 times, the niobium content was confirmed to be 0.76% (TiN substrate) and 0.27% (SiCN substrate), and the selectivity was confirmed to be 2.8:1 (see Figs. 8 and 9).

[0156]

[0157] - Example 2 - Surface oxidation treatment + SDA (surface dependent adsorption) + ALE (atomic layer etch)

[0158]

[0159] The first process activated the surfaces of the SiCN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through an O3 surface treatment process. The process temperature was 340°C and lasted for 10 minutes.

[0160]

[0161] In the second process, niobium precursor was adsorbed on SiCN substrate and TiN substrate through SDA process, respectively. The process temperature was 220 ℃, and no reactants were used.

[0162]

[0163] The third process supplied Trimethyl Orthoformate as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0164]

[0165] The process of supplying niobium precursor and etching initiator is as follows, and process 1) below is the first process, processes 2)-3) are the second process, and processes 4)-7) are the third process (see Figures 1 and 2).

[0166]

[0167] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiCN substrate and TiN substrate.

[0168] 2) Using Ar as a carrier gas, the niobium precursor TBTEMNb is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0169] 3) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0170] 4) Using Ar as a carrier gas, the etching initiator Trimethyl Orthoformate is supplied to the reaction chamber and adsorbed on the SiCN substrate and TiN substrate.

[0171] 5) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0172] 6) Supply O3 gas to the reaction chamber to activate etching.

[0173] 7) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0174]

[0175] After the first process was performed for 10 minutes, the second process was repeated 100 times, and the third process was repeated 100 times, the niobium content was confirmed to be 0.86% (TiN substrate) and 0.18% (SiCN substrate), and the niobium in the non-growth region was confirmed to be reduced by approximately 33% compared to Comparative Example 2, resulting in a selectivity of 4.8:1 (see Figs. 8 and 10).

[0176]

[0177] In conclusion, when the O3 surface treatment process is applied, the selective etching effect of the non-metallic thin film SiCN substrate over the metal thin film TiN substrate is enhanced.

[0178]

[0179] - Comparative Example 3 - SDA (surface dependent adsorption) + adsorption promotion + ALE (atomic layer etch)

[0180]

[0181] Unlike Example 3 described below, the surface treatment process corresponding to the first process was not performed.

[0182]

[0183] In the second process, niobium precursor was adsorbed on the SiCN substrate (non-metallic thin film, non-growth area) and the TiN substrate (metallic thin film, growth area) through the SDA process, respectively. The process temperature was 300°C, and O2 gas was used as the accelerator.

[0184]

[0185] The third process supplied Trimethyl Orthoformate as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0186]

[0187] The process of supplying niobium precursor and etching initiator is as follows, and processes 1)-4) below were carried out as the second process, and processes 5)-8) were carried out as the third process.

[0188]

[0189] 1) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0190] 2) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0191] 3) Supply O2 gas to the reaction chamber to promote niobium precursor adsorption.

[0192] 4) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0193] 5) Using Ar as a carrier gas, the etching initiator Trimethyl Orthoformate is supplied to the reaction chamber and adsorbed on the SiCN substrate and TiN substrate.

[0194] 6) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0195] 7) Supply O3 gas to the reaction chamber to activate etching.

[0196] 8) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0197]

[0198] When the second process was repeated 100 times and the third process was repeated 100 times, the niobium content was confirmed to be 1.17% (TiN substrate) and 0.23% (SiCN substrate), and the selectivity was confirmed to be 5.1:1 (see Figs. 11 and 12).

[0199]

[0200] - Example 3 - Surface oxidation treatment + SDA (surface dependent adsorption) + adsorption promotion + ALE (atomic layer etch)

[0201]

[0202] The first process activated the surfaces of the SiCN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through an O3 surface treatment process. The process temperature was 340°C and lasted for 10 minutes.

[0203]

[0204] In the second process, niobium precursor was adsorbed on SiCN substrate and TiN substrate through SDA process, respectively, at a process temperature of 300 ℃ and O2 gas was used as a catalyst.

[0205]

[0206] The third process supplied Trimethyl Orthoformate as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0207]

[0208] The process of supplying niobium precursor and etching initiator is as follows, and process 1) below is the first process, processes 2)-5) are the second process, and processes 6)-9) are the third process (see Figures 3 and 4).

[0209]

[0210] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiCN substrate and TiN substrate.

[0211] 2) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0212] 3) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0213] 4) Supply O2 gas to the reaction chamber to promote niobium precursor adsorption.

[0214] 5) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0215] 6) Using Ar as a carrier gas, the etching initiator Trimethyl Orthoformate is supplied to the reaction chamber and adsorbed on the SiCN substrate and TiN substrate.

[0216] 7) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0217] 8) Supply O3 gas to the reaction chamber to activate etching.

[0218] 9) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0219]

[0220] After the first process was performed for 10 minutes, the second process was repeated 100 times, and the third process was repeated 100 times, the niobium content was confirmed to be 1.04% (TiN substrate) and 0.17% (SiCN substrate), and the niobium in the non-growth region was confirmed to be reduced by approximately 26% compared to Comparative Example 3, resulting in a selectivity of 6.1:1 (see Figs. 11 and 13).

[0221]

[0222] In conclusion, when the O3 surface treatment process is applied, the selective etching effect of the non-metallic thin film SiCN substrate over the metal thin film TiN substrate is enhanced.

[0223]

[0224] Figures 14 and 15 are graphs showing changes in the content and selectivity of niobium in the non-growth region depending on the presence or absence of O3 surface treatment, respectively. As shown in Figure 14, it can be confirmed that the content of niobium in the non-growth region (SiCN) decreases depending on the O3 surface treatment, and as shown in Figure 15, it can be confirmed that the selectivity is improved due to the O3 surface treatment.

[0225]

[0226] - Comparative Example 4 - Surface oxidation treatment + SDA (surface dependent adsorption) + adsorption promotion

[0227]

[0228] The first process activated the surfaces of SiCN and SiBN substrates (non-metallic thin films, non-growth areas) and TiN substrates (metallic thin films, growth areas) through an O3 surface treatment process. The process temperature was 300°C and lasted for 10 minutes.

[0229]

[0230] In the second process, niobium precursor was adsorbed on SiCN substrate, SiBN substrate, and TiN substrate through SDA process, respectively, at a process temperature of 300°C and O2 gas was used as a catalyst.

[0231]

[0232] Unlike Example 4 described below, the etching initiator supply step corresponding to the third process was not performed.

[0233]

[0234] The process of supplying niobium precursor and etching initiator is as follows, with process 1) below as the first process and processes 2)-5) as the second process.

[0235]

[0236] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiCN substrate, SiBN substrate, and TiN substrate.

[0237] 2) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate, SiBN substrate, and TiN substrate.

[0238] 3) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0239] 4) Supply O2 gas to the reaction chamber to promote niobium precursor adsorption.

[0240] 5) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0241]

[0242] After the first process was performed for 10 minutes and the second process was repeated 100 times, the niobium content was confirmed to be 4.9% (TiN substrate), 0.8% (SiCN substrate), and 1.0% (SiBN substrate) (see Fig. 16).

[0243]

[0244] - Example 4 - Surface oxidation treatment + SDA (surface dependent adsorption) + adsorption promotion + ALE (atomic layer etch)

[0245]

[0246] The first process activated the surfaces of SiCN and SiBN substrates (non-metallic thin films, non-growth areas) and TiN substrates (metallic thin films, growth areas) through an O3 surface treatment process. The process temperature was 300°C and lasted for 10 minutes.

[0247]

[0248] In the second process, niobium precursor was adsorbed on SiCN substrate, SiBN substrate, and TiN substrate through SDA process, respectively, at a process temperature of 300°C and O2 gas was used as a catalyst.

[0249]

[0250] In the third process, dimethylformamide dimethyl acetal (DFDA) was supplied as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0251]

[0252] The process of supplying niobium precursor and etching initiator is as follows, and process 1) below is the first process, processes 2)-5) are the second process, and processes 6)-9) are the third process (see Figures 3 and 4).

[0253]

[0254] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiCN substrate, SiBN substrate, and TiN substrate.

[0255] 2) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiCN substrate, SiBN substrate, and TiN substrate.

[0256] 3) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0257] 4) Supply O2 gas to the reaction chamber to promote niobium precursor adsorption.

[0258] 5) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0259] 6) Using Ar as a carrier gas, the etching initiator Dimethylformamide dimethyl acetal (DFDA) is supplied to the reaction chamber and adsorbed on the SiCN substrate, SiBN substrate, and TiN substrate.

[0260] 7) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0261] 8) Supply O3 gas to the reaction chamber to activate etching.

[0262] 9) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0263]

[0264] After the first process is performed for 10 minutes, the second process is repeated 100 times and the third process is repeated 10 times, the niobium content is confirmed to be 1.8% (TiN substrate), 0.0% (SiCN substrate), and 0.1% (SiBN substrate), and it can be confirmed that the niobium in the non-growth area, the SiCN substrate and the SiBN substrate, is reduced compared to Comparative Example 4 (see Figs. 16 and 17).

[0265]

[0266] In conclusion, after changing the etching initiator to Dimethylformamide dimethyl acetal (DFDA), the content of niobium in the non-growth regions, SiCN and SiBN, was minimized, and the selectivity ratio (TiN:SiCN) was confirmed to be 1:0 and the selectivity ratio (TiN:SiBN) was confirmed to be 18:1.

[0267]

[0268] - Comparative Example 5 - Surface oxidation treatment + SDA (surface dependent adsorption) + adsorption promotion

[0269]

[0270] The first process activated the surfaces of the SiCN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through an O3 surface treatment process. The process temperature was 300°C and lasted for 10 minutes.

[0271]

[0272] In the second process, tantalum precursor was adsorbed on SiCN substrate and TiN substrate through SDA process, respectively, at a process temperature of 300 ℃ and O2 gas was used as a catalyst.

[0273]

[0274] Unlike Example 5 described below, the etching initiator supply step corresponding to the third process was not performed.

[0275]

[0276] The tantalum precursor and etching initiator supply process is as follows, with process 1) below as the first process and processes 2)-5) as the second process.

[0277]

[0278] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiCN substrate and TiN substrate.

[0279] 2) Using Ar as a carrier gas, the tantalum precursor EtMeCp-Ta=NtBu(Cl)2 is supplied to the reaction chamber and the tantalum precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0280] 3) Supply Ar gas into the reaction chamber to remove unabsorbed tantalum precursor or byproducts.

[0281]

[0282] *4) Supplying O2 gas to the reaction chamber to promote tantalum precursor adsorption.

[0283] 5) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0284]

[0285] After the first process was performed for 10 minutes and the second process was repeated 100 times, the tantalum content was confirmed to be 4.5% (TiN substrate) and 1.1% (SiCN substrate), and the selectivity was confirmed to be 4.3:1 (see Fig. 18).

[0286]

[0287] - Example 5 - Surface oxidation treatment + SDA (surface dependent adsorption) + adsorption promotion + ALE (atomic layer etch)

[0288]

[0289] The first process activated the surfaces of the SiCN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through an O3 surface treatment process. The process temperature was 300°C and lasted for 10 minutes.

[0290]

[0291] In the second process, tantalum precursor was adsorbed on SiCN substrate and TiN substrate through SDA process, respectively, at a process temperature of 300 ℃ and O2 gas was used as a catalyst.

[0292]

[0293] In the third process, dimethylformamide dimethyl acetal (DFDA) was supplied as an etching initiator to the upper substrate. The process temperature was 300 ℃, and O3 gas was used as the reactant.

[0294]

[0295] The process of supplying tantalum precursor and etching initiator is as follows, and process 1) below is the first process, processes 2)-5) are the second process, and processes 6)-9) are the third process (see Figures 3 and 4).

[0296]

[0297] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiCN substrate and TiN substrate.

[0298] 2) Using Ar as a carrier gas, the tantalum precursor EtMeCp-Ta=NtBu(Cl)2 is supplied to the reaction chamber and the tantalum precursor is adsorbed on the SiCN substrate and the TiN substrate.

[0299] 3) Supply Ar gas into the reaction chamber to remove unabsorbed tantalum precursor or byproducts.

[0300] 4) Supplying O2 gas to the reaction chamber to promote tantalum precursor adsorption.

[0301] 5) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0302] 6) Using Ar as a carrier gas, the etching initiator Dimethylformamide dimethyl acetal (DFDA) is supplied to the reaction chamber and adsorbed on the SiCN substrate and TiN substrate.

[0303] 7) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0304] 8) Supply O3 gas to the reaction chamber to activate etching.

[0305] 9) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0306]

[0307] After the first process was performed for 10 minutes, the second process was repeated 100 times and the third process was repeated 50 times, and the tantalum content was confirmed to be 3.2% (TiN substrate) and 0.2% (SiCN substrate), and the tantalum in the non-growth region, SiCN, was reduced by approximately 81% compared to Comparative Example 5, and the selectivity was confirmed to be 15.9:1 (see FIGS. 18 and 19).

[0308]

[0309] Fig. 20 is a flowchart showing a thin film processing method according to another embodiment of the present invention, and Fig. 21 is a graph schematically showing a supply cycle according to another embodiment of the present invention. Unlike the previously described embodiment, after the precursor is adsorbed on the thin film formed on the substrate and the unadsorbed precursor or byproduct is removed through a purge gas, an etching initiator and a promoter are supplied. Through this, the adsorption and reaction of the precursor are induced in the growth region, and the reactivity between the growth / non-growth region is controlled based on the surface oxidation state by the etching initiator and O3 in the non-growth region, thereby optimizing surface-dependent adsorption. Preferably, the promoter can be replaced with O3, O2, or H2O.

[0310]

[0311] - Comparative Example 6 - Surface oxidation treatment + SDA (surface dependent adsorption) + adsorption promotion

[0312]

[0313] The first process activated the surfaces of the SiBN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through an O3 surface treatment process. The process temperature was 300°C and lasted for 10 minutes.

[0314]

[0315] In the second process, niobium precursor and etching initiator were repeatedly supplied onto the SiBN substrate and the TiN substrate, respectively, at a process temperature of 300°C and O3 gas was used as the reactant.

[0316]

[0317] *

[0318] Unlike Example 6 described below, the etching initiator supply step corresponding to the third process was not performed.

[0319]

[0320] The process of supplying niobium precursor and etching initiator is as follows, and process 1) below was carried out as the first process, and processes 2)-7) were carried out as the second process (see Figures 20 and 21).

[0321]

[0322] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiBN substrate and TiN substrate.

[0323] 2) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiBN substrate and the TiN substrate.

[0324] 3) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0325] 4) Using Ar as a carrier gas, the etching initiator Dimethylformamide dimethyl acetal (DFDA) is supplied to the reaction chamber and adsorbed on the SiBN substrate and TiN substrate.

[0326] 5) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0327] 6) Supply O3 gas to the reaction chamber to promote niobium precursor adsorption.

[0328] 7) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0329]

[0330] After the first process was performed for 10 minutes and the second process was repeated 100 times, the niobium content was confirmed to be 5.7% (TiN substrate) and 0.2% (SiBN substrate), and the selectivity was confirmed to be 28.5:1 (see Fig. 22).

[0331]

[0332] - Example 6 - Surface oxidation treatment + SDA (surface dependent adsorption) + adsorption promotion + ALE (atomic layer etch)

[0333]

[0334] The first process activated the surfaces of the SiBN substrate (non-metallic thin film, non-growth region) and the TiN substrate (metallic thin film, growth region) through an O3 surface treatment process. The process temperature was 300°C and lasted for 10 minutes.

[0335]

[0336] In the second process, niobium precursor and etching initiator were repeatedly supplied onto the SiBN substrate and the TiN substrate, respectively, at a process temperature of 300°C and O3 gas was used as the reactant.

[0337]

[0338] In the third process, dimethylformamide dimethyl acetal (DFDA) was supplied as an etching initiator to the upper substrate. The process temperature was 340 ℃, and O3 gas was used as the reactant.

[0339]

[0340] The process of supplying niobium precursor and etching initiator is as follows, and process 1) below is the first process, processes 2)-7) are the second process, and processes 8)-11) are the third process (see Figures 20 and 21).

[0341]

[0342] 1) Supply O3 to the reaction chamber and activate the surfaces of the SiBN substrate and TiN substrate.

[0343] 2) Using Ar as a carrier gas, the niobium precursor EtMeCp-Nb=NtBu(Cl)2 is supplied to the reaction chamber and the niobium precursor is adsorbed on the SiBN substrate and the TiN substrate.

[0344] 3) Supply Ar gas into the reaction chamber to remove unabsorbed niobium precursor or byproducts.

[0345] 4) Using Ar as a carrier gas, the etching initiator Dimethylformamide dimethyl acetal (DFDA) is supplied to the reaction chamber and adsorbed on the SiBN substrate and TiN substrate.

[0346] 5) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0347] 6) Supply O3 gas to the reaction chamber to promote niobium precursor adsorption.

[0348] 7) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0349] 8) Using Ar as a carrier gas, the etching initiator Dimethylformamide dimethyl acetal (DFDA) is supplied to the reaction chamber and adsorbed on the SiBN substrate and TiN substrate.

[0350] 9) Supply Ar gas into the reaction chamber to remove unabsorbed etching initiator or byproducts.

[0351]

[0352] *10) Activate etching by supplying O3 gas to the reaction chamber.

[0353] 11) Supply Ar gas into the reaction chamber to remove unreacted substances or byproducts.

[0354]

[0355] After the first process was performed for 10 minutes, the second process was repeated 100 times and the third process was repeated 10 times, the niobium content was confirmed to be 3.2% (TiN substrate) and 0.0% (SiBN substrate), and the selectivity was confirmed to be 1:0 (see Figs. 22 and 23).

[0356]

[0357] In conclusion, the selectivity was optimized by adding the etching initiator in the form of deposition and etching in the second process, and then the niobium content in the non-growth region of the SiBN substrate was minimized by using Dimethylformamide dimethyl acetal (DFDA) as the etching initiator in the third process.

[0358]

[0359] Meanwhile, in Comparative Examples 4 to 6, it was confirmed that a small amount of metal oxide remained in the non-growth region when the surface oxidation process and SDA process were applied. However, in Examples 4 to 6, it was confirmed that the phenomenon of metal oxide remaining in the non-growth region was significantly reduced by applying the ALE technology.

[0360]

[0361] These results confirm that the ALE technology plays a role in removing residual metal oxide, thereby minimizing metal oxide residue in non-growth regions. Therefore, as confirmed through the embodiments of the present invention, when applying the surface oxidation process and the SDA process, by using the ALE technology in parallel, the metal oxide residue in the non-growth region can be minimized, and as a result, the selectivity in the deposition process can be significantly improved. As a result, the process controllability is superior to that of existing technologies, and a technology can be secured that can deposit a uniform thin film in a desired region during the process of manufacturing a highly integrated device.

[0362]

[0363] 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.

[0364] The present invention can be applied to various types of semiconductor manufacturing methods.

Claims

1. A step of supplying a surface oxidizer into the chamber where the substrate is placed to treat the substrate; A step of supplying a precursor into the interior of the chamber and adsorbing the precursor onto the substrate; A step of purging the interior of the chamber; 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 supplying a reactant into the interior of the chamber to form a thin film and activate the etching initiator; and A thin film processing method comprising a step of purging the interior of the chamber.

2. A step of supplying a surface oxidizer into the chamber where the substrate is placed to treat the substrate; A step of supplying a precursor into the interior of the chamber and adsorbing the precursor onto the substrate; A step of purging the interior of the chamber; A step of supplying a promoting substance into the interior of the chamber; A step of purging the interior of the chamber; 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 supplying a reactant into the interior of the chamber to form a thin film and activate the etching initiator; and A thin film processing method comprising a step of purging the interior of the chamber.

3. A step of supplying a surface oxidizer into the chamber where the substrate is placed to treat the substrate; A step of supplying a precursor into the interior of the chamber and adsorbing the precursor onto the substrate; A step of purging the interior of the chamber; A step of supplying a first etching initiator into the interior of the chamber; A step of purging the interior of the chamber; A step of supplying a promoting substance into the interior of the chamber; A step of purging the interior of the chamber; A step of supplying a second etching initiator into the interior of the chamber; A step of purging the interior of the chamber; A step of supplying a reactant into the interior of the chamber to form a thin film and activate the etching initiator; and A thin film processing method comprising a step of purging the interior of the chamber.

4. In any one of paragraphs 1 to 3, A thin film treatment method wherein the surface oxidizing agent is any one of O3, O2, and H2O.

5. 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.

6. In any one of paragraphs 1 to 3, 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.

7. In any one of paragraphs 1 to 3, A method for treating 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 to 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, an alkoxy group having 0 to 4 carbon atoms, and a dialkylamine group having 0 to 4 carbon atoms.

8. In any one of paragraphs 1 to 3, A method for treating a thin film, wherein the etching initiator is any one of dichloromethyl methyl ether (DCMME) and 1-chloromethyl ethyl ether (1-CMEE).

9. In any one of paragraphs 1 to 3, The above thin film is a thin film processing method having one of Al, Ti, Hf, Nb, Ta, Mo, W, Zr, Ru, Sn, and Cr 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 any one of a metal film, a metal oxide, a metal nitride, a metal sulfide, silicon nitride, and silicon oxide.

11. 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.

12. 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.

13. 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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