A method of atomic layer deposition of a Ru-containing thin film

Abstract

The present application belongs to the technical field of material deposition, and particularly relates to a method for atomic layer deposition of a Ru-containing film. First, a seed layer deposition cycle is performed to form a required seed layer on a substrate, and then a conventional deposition cycle is performed to grow a Ru-containing layer; the seed layer deposition cycle comprises a first Ru precursor pulse, a first co-reactant pulse and a purge pulse performed in sequence, wherein the first Ru precursor pulse and the first co-reactant pulse overlap for a set time; the conventional deposition cycle comprises a second Ru precursor pulse, a precursor pulse purge, a second co-reactant pulse and a co-reactant pulse purge performed in sequence and independently. The present application improves the deposition method of the seed layer in ALD deposition. By overlapping the pulses, the nucleation delay is reduced, and by optimizing the reaction conditions, the occurrence of CVD-like gas phase reactions is avoided, achieving the dual effects of shortening the incubation period and reducing the roughness.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of material deposition, and particularly relates to a method for atomic layer deposition of a Ru-containing thin film. BACKGROUND

[0002] Ruthenium (Ru) is a noble metal with good thermal stability, chemical stability, low resistivity (~7.1 μΩ·cm), high work function (4.7 eV), low solubility in copper (Cu) and strong adhesion to Cu. Due to these good physical, chemical and electrical properties, Ru thin films have attracted extensive attention in a series of applications in semiconductor devices, such as electrodes of capacitors, transistor gates and seed layers for copper electroplating in dynamic random access memory (DRAM).

[0003] With the increasing demand for chip shrinkage size, the growth requirements for ruthenium thin films (including ruthenium-containing thin films) are also increasing. Such applications require deposition techniques with high process controllability, which can achieve the deposition of ultrathin films and maintain uniformity over a large area. In these aspects, atomic layer deposition (ALD) is a very suitable solution. Since ALD uses a self-limiting growth mode of surface saturation reaction, it can achieve atomic-level thickness control, thereby providing excellent thin film quality and high thickness uniformity.

[0004] However, the ALD process of Ru usually experiences a relatively long incubation period in the initial stage of thin film deposition, which is related to the delayed nucleation of thin film material on the growth surface, i.e. no reactant deposition during the initial growth period.

[0005] It has been reported in existing studies that using divalent Ru (EtCp)2 and O2 as precursors and second reactants to grow Ru on tantalum nitride (TaN) substrates requires 100 incubation cycles (S-J. Park, Microelectron Eng. 85 (2008) 39); using trivalent Ru (thd)3 and O2 as precursors and second reactants to grow Ru on Al2O3 substrates has 250 incubation cycles (T. Aaltonen. Chem. Vap. Depsition 10 (2004) 217); using zero-valent EBBDRu and O2 as precursors and second reactants, and using a P-type Si (100) wafer coated with 100 nm thick thermally grown SiO2 as a substrate, Ru thin film growth requires 15 incubation cycles (S. Yeo. Microelectronic Engineering 137 (2015) 19). Longer incubation periods not only affect the deposition time, but also cause the roughness of the thin film to increase and the resistivity to increase, especially in the case of thin film thickness requirements.

[0006] Therefore, it is still a technical problem to provide a method for atomic layer deposition of Ru capable of improving the nucleation delay phenomenon in the initial growth of Ru. SUMMARY

[0007] To solve the above technical problems, the present application provides a method for atomic layer deposition of Ru-containing thin film.

[0008] The technical solutions adopted by the present application are as follows:

[0009] A method for atomic layer deposition of Ru-containing thin film, first performing a seed layer deposition cycle, after forming a desired seed layer on a substrate, performing a conventional deposition cycle to grow a Ru-containing layer; the seed layer deposition cycle includes a first Ru precursor pulse, a first co-reactant pulse and a purge pulse performed in sequence, wherein the first Ru precursor pulse and the first co-reactant pulse have a set time overlap; the conventional deposition cycle includes a second Ru precursor pulse, a precursor pulse purge, a second co-reactant pulse and a co-reactant pulse purge performed in sequence and independently.

[0010] Preferably, the pressure in the reaction chamber is 0.1-10 Torr.

[0011] Preferably, in the seed layer deposition cycle, the single first Ru precursor pulse time is 2-5 s, the single first co-reactant pulse time is 2-5 s, and the set time overlap is at least 1 s, preferably 2-5 s.

[0012] Preferably, in the seed layer deposition cycle, the flow rate of the first co-reactant into the reaction chamber is 50-300 sccm, more preferably 80-200 sccm; the carrier gas carrying the first Ru precursor into the reaction chamber has a flow rate of 20-200 sccm, more preferably 40-100 sccm.

[0013] Preferably, the seed layer thickness is 1-10 nm, more preferably 2-5 mm.

[0014] Preferably, the first and second Ru precursors are selected from the group consisting of 0-valent ethylbenzene (1-ethyl-1,4-cyclohexadiene) ruthenium (EBECHRu), (1-methyl-1,4-cyclohexadiene)tricarbonylruthenium, (2,3-dimethyl-1,3-butadiene)tricarbonylruthenium (Ru(DMBD)(CO)3), 2-valent bis(ethylcyclopentadienyl)ruthenium (Ru(EtCp)2), bis(2,4-dimethylpentadiene)ruthenium (Ru(DMPD)2), biscyclopentadienyl ruthenium (Ru(Cp)2), 3-valent tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium (Ru(thd)3 / Ru(tmhd)3), tris(acetylacetonato)ruthenium (Ru(acac)3); more preferably, ethylbenzene (1-ethyl-1,4-cyclohexadiene) ruthenium, bis(2,4-dimethylpentadiene)ruthenium, bis(ethylcyclopentadienyl)ruthenium.

[0015] Preferably, the first and second co-reactants are selected from the group consisting of O2, NH3, H2, t BuNH2, N2H4, SiH4, Si2H6, B2H4; more preferably, O2.

[0016] According to the above Ru precursors and co-reactants, the Ru-containing thin films prepared by the present application include, but are not limited to, Ru elemental thin films, RuO2thin films, RuN or Ru-doped nitrogen-containing thin films, RuSi alloy or S-doped Ru thin films, RuB alloy or B-doped Ru thin films.

[0017] Preferably, in the conventional deposition cycle, the single second Ru precursor pulse time is 2-10 s, and the single second co-reactant pulse time is 5-20 s.

[0018] Preferably, in the conventional deposition cycle, the flow rate of the second co-reactant into the reaction chamber is 100-500 sccm; the carrier gas carrying the second Ru precursor into the reaction chamber has a flow rate of 40-150 sccm.

[0019] Preferably, the deposition temperature of the seed layer deposition cycle is 185-300°C, and the deposition temperature of the conventional deposition cycle is 150-300°C.

[0020] The substrate includes a semiconductor material, a dielectric material, or a metal material; the semiconductor material includes any one or more of Si and Ge, the dielectric material includes any one or more of SiO2, HfO2, ZrO2, La2O3, Al2O3, and the metal material includes any one or more of Ti, Al, Ni, Co, TiN, and TaN; the substrate material is more preferably Si, SiO2, TiN, and TaN.

[0021] Preferably, the substrate is a planar substrate or a high aspect ratio (HAR) substrate.

[0022] Preferably, it includes the following steps:

[0023] S1. Place the substrate in the reaction chamber, evacuate the chamber, and then adjust the reaction chamber to the set temperature and set pressure.

[0024] S2. Generate the seed layer, selected from any of the following schemes:

[0025] A) Adjust the flow rate and simultaneously introduce the first Ru precursor and the first co-reactant into the reaction chamber using carrier gas. After a set pulse time m1, perform pulse purging. Repeat the operation until the desired seed layer is obtained.

[0026] B) Adjust the flow rate and introduce the first Ru precursor into the reaction chamber using carrier gas. After a set pulse time m2, introduce the first co-reactant. After another set pulse time m3, perform pulse purging. Repeat the operation until the desired seed layer is obtained.

[0027] S3. Growth of Ru-containing thin film: Adjust the flow rate, and introduce the second Ru precursor into the reaction chamber through the carrier gas. After a set pulse time n1, perform pulse purging. Then introduce the second co-reactant and perform pulse purging after a set pulse time n2. Repeat the operation until the desired Ru-containing thin film is obtained.

[0028] Preferably, in Scheme B, the total pulse time of the first Ru precursor is m4, the set pulse time m1, the set pulse time m3 and the total pulse time m4 are 2~5s, the set pulse time m2 is 0~5s but not 0, and m2<m4; the set pulse time n1 is 2~10s, the set pulse time n2 is 5~30s, and the pulse purge time is 8~20s.

[0029] The beneficial effects of this invention are as follows:

[0030] An improved seed layer deposition method in ALD (Atomic Layer Deposition) is presented. During seed layer deposition, by setting the first precursor and first co-reactant to overlap in pulses, the nucleation delay problem is significantly reduced. In this application, this pulsed deposition method with coexisting precursors and co-reactants resembles CVD (Chemical Vapor Deposition). It is generally believed in the art that CVD deposition, due to non-self-limiting growth and side reactions, is detrimental to controlling film roughness. Therefore, in the preparation of fine films such as Ru, continuous reactions caused by the mixing of precursors and co-reactants are avoided as much as possible. This application breaks with this conventional thinking by introducing a CVD-like technique, which is inherently detrimental to film roughness, in reverse. By optimizing the types of seed layer precursors and co-reactants, pulse overlap time, deposition temperature, and other conditions, CVD-like vapor phase reactions are avoided, thus shortening the incubation cycle and achieving the dual effect of reducing roughness. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the method for growing a seed layer in this application, where Figure (a) corresponds to scheme A and Figure (b) corresponds to scheme B;

[0032] Figure 2 This is a schematic diagram of the method for growing Ru thin films in this application.

[0033] Figure 3 These are TEM images of the Ru seed layer formed after 40 cycles and the ruthenium-containing thin film formed after 100 cycles in Example 1.

[0034] Figure 4 This is a TEM image of the ruthenium thin film formed after 150 cycles in Comparative Example 2. Detailed Implementation

[0035] Unless otherwise stated, the terms used herein have the meanings commonly understood by those skilled in the art.

[0036] The technical solution of the present invention will be described in more detail below with reference to embodiments:

[0037] Example 1

[0038] See Figures 1-2 The method for atomic layer deposition of Ru-containing thin films comprises the following steps:

[0039] S1. After cleaning and drying the Si substrate, place it in the reaction chamber and fix it. After evacuating the vacuum, adjust the temperature of the reaction chamber to 185℃. Heat the Ru(DMPD)2 source bottle to 65℃ and connect it to the reaction chamber through the ALD valve and pipeline. The base pressure of the reaction chamber is 1 Torr.

[0040] S2. Seed layer growth:

[0041] S21. The first Ru precursor Ru(DMPD)2 and the first co-reactant O2 are simultaneously introduced into the reaction chamber by Ar carrier gas, with an Ar flow rate of 100 sccm, an O2 flow rate of 200 sccm, and a pulse time m1 of 2 s.

[0042] S22. Purge the pipeline and chamber with Ar for 15 seconds at a flow rate of 100 sccm.

[0043] Steps S21-S22 above constitute one deposition cycle. Repeat 40 deposition cycles to obtain the desired seed layer.

[0044] S3. Growth of Ru-containing thin films:

[0045] S31. The second Ru precursor Ru (DMPD)2 is carried into the cavity by Ar carrier gas, with an Ar flow rate of 100 sccm and a pulse time n1 of 5 s;

[0046] S32. Use Ar to purge the pipeline and chamber for 15 seconds at an Ar flow rate of 100 sccm.

[0047] S33. The second co-reactant O2 is introduced into the cavity by Ar carrier gas, with an Ar flow rate of 100 sccm, a pulse time n2 of 10 s, and an O2 flow rate of 200 sccm, to form a Ru layer;

[0048] S34. Use Ar to purge the pipeline and chamber for 15 seconds at a flow rate of 100 sccm.

[0049] Steps S31-S34 above constitute one deposition cycle. Repeat steps S31-S34 until the desired film thickness is achieved.

[0050] Example 2

[0051] See Figures 1-2 The method for atomic layer deposition of Ru-containing thin films comprises the following steps:

[0052] S1. After cleaning and drying the Si substrate, place it in the reaction chamber and fix it. After evacuating, adjust the temperature of the reaction chamber to 225°C. Heat the EBECHRu source bottle to 100°C and connect it to the reaction chamber through the ALD valve and pipeline. The base pressure of the reaction chamber is 0.5 Torr.

[0053] S2. Seed layer growth:

[0054] S21. The first Ru precursor EBECHRu is carried into the reaction chamber by Ar carrier gas. The pulse time m4 is 3s and the pulse time m2 is set to 1s. That is, at the end of the first second of EBECHRu introduction, the first co-reactant O2 is introduced into the reaction chamber. The Ar flow rate is 50sccm, the O2 flow rate is 100sccm, and the pulse time m3 is 2s.

[0055] S22. Purge the pipeline and chamber with Ar for 10 seconds at a flow rate of 50 sccm.

[0056] Steps S21-S22 above constitute one deposition cycle. Repeat 40 deposition cycles to obtain the desired seed layer.

[0057] S3. Growth of Ru-containing thin films:

[0058] S31. The second Ru precursor Ru (DMPD)2 is introduced into the cavity by Ar carrier gas, with an Ar flow rate of 50 sccm and a pulse time n1 of 7 s.

[0059] S32. Purge the pipeline and chamber with Ar for 10 seconds at a flow rate of 50 sccm.

[0060] S33. The second co-reactant O2 is introduced into the cavity by Ar carrier gas, with an Ar flow rate of 50 sccm, a pulse time n2 of 30 s, and an O2 flow rate of 500 sccm, to form a RuOx layer;

[0061] S34. Use Ar to purge the pipeline and chamber for 10 seconds at a flow rate of 50 sccm.

[0062] Steps S31-S34 above constitute one deposition cycle. Repeat steps S31-S34 until the desired film thickness is achieved.

[0063] Example 3

[0064] See Figures 1-2 The method for atomic layer deposition of Ru-containing thin films comprises the following steps:

[0065] S1. After cleaning and drying the Si substrate, place it in the reaction chamber and fix it. After evacuating the vacuum, adjust the temperature of the reaction chamber to 230℃. Heat the Ru(EtCp)2 source bottle to 100℃ and connect it to the reaction chamber through the ALD valve and pipeline. The base pressure of the reaction chamber is 0.5 Torr.

[0066] S2. Seed layer growth:

[0067] S21. The first Ru precursor Ru(EtCp)2 is introduced into the reaction chamber by Ar carrier gas, and the pulse time m4 is 5s; the pulse time m2 is set to 2s, that is, at the end of the 2s of Ru(EtCp)2 introduction, the first co-reactant O2 is introduced into the reaction chamber, the Ar flow rate is 40sccm, the O2 flow rate is 80sccm, and the pulse time m3 is 5s;

[0068] S22. Purge the pipeline and chamber with Ar for 8 seconds at a flow rate of 40 sccm.

[0069] Steps S21-S22 above constitute one deposition cycle. Repeat 60 deposition cycles to obtain the desired seed layer.

[0070] S3. Growth of Ru-containing thin films:

[0071] S31. The second Ru precursor Ru(EtCp)2 is carried into the cavity by Ar carrier gas, with an Ar flow rate of 40 sccm and a pulse time n1 of 10 s.

[0072] S32. Use Ar to purge the pipeline and chamber for 20 seconds at a flow rate of 40 sccm.

[0073] S33. The second co-reactant O2 is introduced into the cavity by Ar carrier gas, with an Ar flow rate of 50 sccm, a pulse time n2 of 20 s, and an O2 flow rate of 100 sccm, to form a Ru layer;

[0074] S34. Use Ar to purge the pipeline and chamber for 15 seconds at an Ar flow rate of 40 sccm.

[0075] Steps S31-S34 above constitute one deposition cycle. Repeat steps S31-S34 until the desired film thickness is achieved.

[0076] Comparative Example 1

[0077] A method for atomic layer deposition of Ru-containing thin films is basically the same as that in Example 1, except that there is no seed layer deposition step.

[0078] Comparative Example 2

[0079] A method for atomic layer deposition of Ru-containing thin films is basically the same as that in Example 1, except that there is no seed layer deposition step, and the substrate is treated with 200W NH3 plasma for 5 minutes before depositing the Ru-containing layer, and then the substrate surface is treated with 100sccmO3 for 10 minutes.

[0080] Comparative Example 3

[0081] A method for atomic layer deposition of Ru-containing thin films is basically the same as in Example 3, except that there is no seed layer deposition step.

[0082] Comparative Example 4

[0083] A method for atomic layer deposition of Ru-containing thin films is basically the same as in Example 1, except that the number of seed layer deposition cycles is adjusted to 100.

[0084] Comparative Example 5

[0085] A method for atomic layer deposition of Ru-containing thin films is basically the same as in Example 1, except that the seed layer is formed as follows:

[0086] S21. Ru(DMPD)2 is introduced into the cavity by Ar carrier gas, with an Ar flow rate of 100 sccm and a pulse duration of 2s;

[0087] S22. O2 is introduced into the cavity by carrying Ar carrier gas, with an Ar flow rate of 200 sccm and a pulse duration of 2s;

[0088] S23. Use Ar to purge the pipeline and chamber for 15 seconds at an Ar flow rate of 100 sccm.

[0089] Steps S21-S23 above constitute one deposition cycle. Repeat 40 deposition cycles to obtain the desired seed layer.

[0090] test

[0091] 1. Nucleation delay: The film thickness at different deposition cycles was measured using an ellipsometry to determine whether there was a film formation delay in the initial growth stage.

[0092] 2. Film surface roughness: The surface roughness of the film is characterized using atomic force microscopy (AFM).

[0093] 3. The morphology of the thin film was measured using a transmission electron microscope (TEM).

[0094] result

[0095] The film thickness and corresponding film roughness results of ruthenium with different deposition cycles in the examples and comparative examples are shown in Tables 1-3.

[0096] Table 1. Effect of different deposition cycle numbers on ruthenium film thickness in Examples 1-3

[0097] ;

[0098] Table 2 shows the effect of different deposition cycle numbers on ruthenium film thickness in Comparative Examples 1-3.

[0099] ;

[0100] Table 3 shows the effect of different deposition cycle numbers on ruthenium film thickness in Comparative Examples 4-5.

[0101] ;

[0102] By comparing Examples 1 and Comparative Examples 1 and 2, as well as Examples 3 and Comparative Example 3, it can be seen that depositing a Ru-containing layer on the Ru seed layer after depositing the Ru seed layer can significantly improve the roughness of the film. As shown in the table, the roughness of Example 1 is 3.68 Å (film thickness 5.2 nm) and 5.15 Å (film thickness 8.1 nm), the roughness of Comparative Example 1 is 8.89 Å (film thickness 6.8 nm) and 9.65 Å (film thickness 9.3 nm), the roughness of Comparative Example 2 is 7.91 Å (film thickness 7.3 nm) and 9.37 Å (film thickness 10.5 nm), the roughness of Example 3 is 8.6 Å (film thickness 7.3 nm) and 15.02 Å (film thickness 11.2 nm), and the roughness of Comparative Example 3 is 9.39 Å (film thickness 5.9 nm) and 19.5 Å (film thickness 8.3 nm).

[0103] The test data also shows that the process method of this application has good initial film formation characteristics. In Example 1, a Ru seed layer of 40 deposition cycles can obtain a Ru layer of 3.1 nm. In Comparative Example 1, no measurable film was obtained after 50 ruthenium deposition cycles. In Comparative Example 2, after treating the substrate with NH3 plasma and O3, the Ru film thickness obtained after 50 deposition cycles was only 1.8 nm. In Example 3, a Ru seed layer of 70 deposition cycles finally obtained a Ru film of 4.5 nm. In Comparative Example 3, no film was generated in the first 50 deposition cycles, and only a Ru film of 2.6 nm was obtained after 100 deposition cycles.

[0104] Figure 3 These are TEM images of the Ru seed layer formed after 40 cycles and the ruthenium-containing thin film formed after 100 cycles in Example 1. Figure 4 The image shows the TEM morphology of the Ru film formed after 150 cycles in Comparative Example 2. It can be seen that the Ru film grown by the method in the example has a smooth surface, while the Ru film grown in the comparative example has a relatively rough surface, indicating that this application can better control the roughness of the prepared film.

[0105] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of the invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for atomic layer deposition of Ru-containing thin films, characterized in that, First, a seed layer deposition cycle is performed to form the desired seed layer on the substrate, and then a conventional deposition cycle is performed to grow a Ru-containing layer. The seed layer deposition cycle includes a first Ru precursor pulse, a first co-reactant pulse, and a purge pulse performed sequentially, wherein the first Ru precursor pulse and the first co-reactant pulse have a set time overlap. The conventional deposition cycle includes a second Ru precursor pulse, a precursor pulse purge, a second co-reactant pulse, and a co-reactant pulse purge performed sequentially and independently. In both the seed layer deposition cycle and the conventional deposition cycle, the reaction chamber pressure is between 0.1 and 10 Torr. In the seed layer deposition cycle, the pulse time for a single first Ru precursor is 2 to 5 s, and the pulse time for a single first co-reactant is 2 to 5 s, with the overlap of the set times being at least 1 s. In the seed layer deposition cycle, the flow rate of the first co-reactant into the reaction chamber is 50 to 300 sccm. The carrier gas carries the first Ru precursor into the reaction chamber at a flow rate of 20 to 200 sccm. The first Ru precursor is independently selected from any one of ethylbenzene(1-ethyl-1,4-cyclohexadiene)ruthenium, (1-methyl-1,4-cyclohexadiene)tricarbonylruthenium, (2,3-dimethyl-1,3-butadiene)tricarbonylruthenium, bis(ethylcyclopentadienyl)ruthenium, bis(2,4-dimethylpentadiene)ruthenium, ruthenium thiocene, tris(2,2,6,6-tetramethyl-3,5-heptanedione)ruthenium, and ruthenium triacetylacetonate; the first co-reactant is independently selected from O2, NH3, H2, and t Any one of BuNH2, N2H4, SiH4, Si2H6, and B2H4.

2. The method for atomic layer deposition of Ru-containing thin films as described in claim 1, characterized in that, The thickness of the seed layer is 1~10 nm.

3. The method for atomic layer deposition of Ru-containing thin films as described in claim 1, characterized in that, The second Ru precursor is independently selected from any one of ethylbenzene(1-ethyl-1,4-cyclohexadiene)ruthenium, (1-methyl-1,4-cyclohexadiene)tricarbonylruthenium, (2,3-dimethyl-1,3-butadiene)tricarbonylruthenium, bis(ethylcyclopentadienyl)ruthenium, bis(2,4-dimethylpentadiene)ruthenium, ruthenium thiocene, tris(2,2,6,6-tetramethyl-3,5-heptanedione)ruthenium, and ruthenium triacetylacetonate; the second co-reaction is independently selected from O2, NH3, H2, ... t Any one of BuNH2, N2H4, SiH4, Si2H6, and B2H4.

4. The method for atomic layer deposition of Ru-containing thin films as described in claim 1, characterized in that, In the conventional deposition cycle, the pulse time for a single second Ru precursor is 2–10 s, and the pulse time for a single second co-reactant is 5–20 s.

5. The method for atomic layer deposition of Ru-containing thin films as described in claim 1, characterized in that, In the conventional deposition cycle, the flow rate of the second co-reactant into the reaction chamber is 100-500 sccm; the carrier gas carries the second Ru precursor into the reaction chamber at a flow rate of 40-150 sccm.

6. The method for atomic layer deposition of Ru-containing thin films as described in claim 1, characterized in that, The deposition temperature of the seed layer deposition cycle is 185~300℃, and the deposition temperature of the conventional deposition cycle is 150~300℃.

7. The method for atomic layer deposition of Ru-containing thin films as described in claim 1, characterized in that, The substrate includes a semiconductor material, a dielectric material, or a metallic material; the semiconductor material includes any one or more of Si and Ge, the dielectric material includes any one or more of SiO2, HfO2, ZrO2, La2O3, and Al2O3, and the metallic material includes any one or more of Ti, Al, Ni, Co, TiN, and TaN.

8. A method for atomic layer deposition of Ru-containing thin films as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Place the substrate in the reaction chamber, evacuate the chamber, and then adjust the reaction chamber to the set temperature and set pressure. S2. Generate the seed layer, selected from any of the following schemes: A) Adjust the flow rate and simultaneously introduce the first Ru precursor and the first co-reactant into the reaction chamber using carrier gas. After a set pulse time m1, perform pulse purging. Repeat the process until the desired seed layer is obtained; B) Adjust the flow rate and introduce the first Ru precursor into the reaction chamber using carrier gas. After a set pulse time m2, introduce the first co-reactant. After another set pulse time m3, perform pulse purging. Repeat the operation until the desired seed layer is obtained. S3. Growth of Ru-containing thin film: Adjust the flow rate, and introduce the second Ru precursor into the reaction chamber through the carrier gas. After a set pulse time n1, pulse purging is performed. Then, the second co-reactant is introduced, and pulse purging is performed after a set pulse time n2. Repeat the operation until the desired Ru-containing film is obtained; the set pulse time m1, set pulse time m2, and set pulse time m3 are 2~5 s, the set pulse time n1 is 2~10 s, the set pulse time n2 is 5~30 s, and the pulse purging time is 8~20 s.

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