Plasma treatment method

Abstract

The present invention provides a vertical pattern in plasma etching of a molybdenum-containing film or a ruthenium-containing film. Provided is a plasma processing method wherein, after a first step in which a molybdenum or ruthenium film is irradiated with a plasma generated using oxygen gas and halogen gas to form a pattern, the following second to fourth steps are repeated up to a prescribed depth: a second step in which a protective film comprising carbon is formed on a pattern side wall by a plasma which uses gas comprising carbon; a third step in which the protective film on a pattern bottom portion is selectively removed and the molybdenum or ruthenium film on the pattern bottom portion is oxidized by a plasma generated using oxygen gas; and a fourth step in which the oxidized molybdenum or ruthenium is etched by a plasma generated using halogen gas. The plasma processing method may further include a fifth step in which the protective film containing carbon formed on the pattern side wall and an altered layer are removed by a plasma comprising hydrogen.

Description

[Technical field]

[0001] The present disclosure relates to a plasma processing method, and more particularly to a plasma processing method for patterns of wiring materials such as Mo (molybdenum) and Ru (ruthenium). [Background technology]

[0002] Due to the miniaturization and three-dimensionalization of functional element products such as semiconductor elements, three-dimensional processing technology for various materials such as gate materials, interlayer films, and metals has become important in the dry etching process in semiconductor manufacturing, and technology is required to control and process complex shapes at the atomic layer level. In particular, miniaturization is also progressing in the wiring process, and the increase in wiring resistance in the future is an issue for the conventionally used Cu (copper) wiring, so the use of Mo (molybdenum) and Ru (ruthenium) as wiring materials is being considered.

[0003] As a method for etching Mo, Non-Patent Document 1 proposes a method in which an unpatterned Mo film is subjected to alternating oxygen (O2) plasma treatment and chlorine (Cl2) plasma treatment, thereby etching several atomic layers of Mo per cycle. When processing a pattern using this method, oxidation also progresses toward the pattern sidewalls by the O2 treatment, and the oxidized Mo is removed by the Cl2 plasma and is etched isotropically, making it difficult to process the pattern in the vertical direction.

[0004] In addition, as a method for etching Mo patterns, a method of plasma etching using a mixed gas containing halogen and oxygen, such as a mixed gas containing chlorine gas (Cl2) and oxygen gas (O2), or a mixed gas containing hydrogen bromide (HBr) and oxygen gas (O2), has been reported. However, as shown in FIG. 2(a), in a device structure having a Mo pattern 102, which is an etched material formed on a substrate 101, and a mask 103 formed on the Mo pattern 102, when plasma etching is performed using a mixed gas containing halogen and oxygen, side etching tends to occur toward the sidewall of the pattern 102, making it difficult to process the pattern into a vertical cross-sectional shape. Furthermore, since Mo is easily oxidized, the surface is easily oxidized during and after etching, which increases the wiring resistance. Therefore, in Non-Patent Document 2, in order to prevent the side walls of the Mo pattern 102 from being etched, a method is proposed in which, during the processing of the Mo pattern 102, a thin SiO2 film 104 is formed by atomic layer deposition (ALD) as a side wall protective film for the Mo pattern 102 formed on the substrate 101, as shown in Figure 2(b), and then the pattern is processed with plasma generated using a mixed gas of Cl2 and O2. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Yebin Lee, et al., Low-temperature plasma atomic layer etching of molybdenum via sequential oxidation and chlorination, Journal of Vacuum Science & Technology A 40, 022602 (2022); https: / / doi.org / 10.1116 / 6.0001603 [Non-Patent Document 2] Stefan Decoster, et al., Patterning challenges for direct metal etch of ruthenium and molybdenum at 32 nm metal pitch and below, Journal of Vacuum Science & Technology B 40, 032802 (2022); https: / / doi.org / 10.1116 / 6.0001791 Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, in order to vertically process fine patterns of Mo or Ru, it is important to have a technology that prevents etching in the direction of the sidewall. With conventional etching using Cl2 or a mixed gas of halogen and O2, etching proceeds in the direction of the sidewall, resulting in poor anisotropy and making it impossible to perform vertical processing. In addition, since the surface of Mo or Ru is very susceptible to oxidation, the molybdenum oxide (MoO x ), or ruthenium oxide (RuO x ) increases the wiring resistance, which was an issue.

[0007] In Non-Patent Document 1, an unpatterned Mo film is etched by several atomic layers per cycle by alternately performing O2 plasma treatment and Cl2 plasma treatment. However, when a pattern is processed using this method, the sidewall of the pattern is easily oxidized by the O2 treatment, and the oxidized Mo is removed by the Cl2 plasma treatment, so that the pattern is also etched in the sidewall direction, making it difficult to process the pattern in the vertical direction.

[0008] In Non-Patent Document 2, in order to prevent etching toward the pattern sidewalls, etching is interrupted midway through pattern processing, and a thin silicon oxide film (SiO2 film) 104 is formed on the pattern surface including the sidewalls of the pattern 102. After that, Mo is etched to a desired depth, using the SiO2 film 104 as a protective film to prevent etching toward the sidewalls.

[0009] However, this method requires removing the SiO2 of the protective film 104 after processing, but it is difficult to remove only the SiO2 of the protective film 104 without etching the Mo on the sidewalls of the Mo pattern 102, which is a fine pattern. In addition, in the process of removing the SiO2 of the protective film 104, the Mo surface is oxidized, and residues and reaction products of the protective film 104 remain at the groove bottoms 201 of the grooves 200 between the Mo patterns 102, which can cause device failures or increase wiring resistance.

[0010] The present disclosure aims to perform vertical processing by suppressing side etching during Mo processing by forming a sidewall protective film of a material that is easily removable after processing. In addition, the present disclosure aims to provide a plasma processing method that etches Mo at a uniform etching rate within the wafer surface and efficiently etches Mo by performing both removal of an unnecessary protective film formed at the bottom of a groove and processing for Mo etching in a Mo vertical processing step. Furthermore, the present disclosure aims to remove the sidewall protective film without scraping the sidewall of the Mo pattern after processing, and to remove residual impurities such as oxides formed on the Mo surface to form a Mo pattern without defects and damage. [Means for solving the problem]

[0011] A plasma processing method for processing and forming a pattern by irradiating a plasma generated by using an oxygen-containing gas and a halogen-containing gas onto a pattern of a Mo (molybdenum) film (or a molybdenum-containing film) or a Ru (ruthenium) film (or a ruthenium-containing film) which is a material to be etched formed on a wafer placed on a stage, comprising: A first step of forming a pattern by irradiating a Mo film or a Ru film with plasma generated by using a mixed gas of a gas containing oxygen (O2) and a gas containing a halogen; a second step of forming a protective film containing carbon (C) on the pattern sidewall by plasma using a gas containing carbon (C) after the first step; a third step of selectively removing the protective film at the bottom of the pattern from the protective film at the sidewalls of the pattern formed in the second step by using plasma generated using a gas containing oxygen (O) and oxidizing the Mo film or Ru film at the bottom of the pattern; a fourth step of generating plasma using a gas containing a halogen gas after the third step, and etching the Mo film or the Ru film oxidized in the third step; The second to fourth steps are repeated to a predetermined depth.

[0012] The plasma processing method can further include a fifth step of removing the protective film containing C formed in the second step, and the altered layer formed on the pattern in the third step and the fourth step, using a plasma containing hydrogen (H). Effect of the Invention

[0013] By forming a protective film containing C on the sidewall of the pattern and etching the bottom of the pattern, the pattern can be processed in the vertical direction. In addition, by oxidizing and removing the unnecessary protective film containing C attached to the bottom of the pattern and oxidizing the Mo film or Ru film on the bottom of the pattern, the Mo film or Ru film can be etched efficiently and at a uniform etching rate within the wafer surface. Furthermore, after etching to the desired depth, it has become possible to remove the protective film containing C and the etching residue on the sidewall of the pattern without progressing the etching of the Mo film or Ru film on the sidewall by processing with plasma containing hydrogen (H2). [Brief description of the drawings]

[0014] [Figure 1] FIG. 2 is a diagram showing an example of a process flow of the plasma processing method of the present disclosure. [Diagram 2] 1A and 1B are explanatory diagrams for explaining the problems of the conventional method, in which (a) shows side etching in the direction of the side wall of the pattern 102, and (b) shows the state in which a sidewall protective film has been formed to prevent side etching in the direction of the side wall of the pattern 102. [Diagram 3] 1 is a diagram showing an example of an apparatus for performing a plasma processing method according to the present disclosure. [Figure 4] 4A to 4C are pattern cross-sectional views illustrating an example of a process flow of the plasma processing method of the present embodiment. [Diagram 5] 5A to 5C are explanatory views of an example of a method for removing a protective film in an oxidation treatment step of the present embodiment. [Figure 6] 1A and 1B are explanatory diagrams of an example of an oxidation treatment step in this embodiment, in which (a) shows the dependence of the etch rate on the oxidation treatment time, (b) shows the dependence of the saturated etch rate (ER1) on the bias power of the oxidation treatment (step S3), and (c) shows the dependence of the oxidation treatment time (T) until etching starts when a C-containing protective film 105 is formed on the bias power of the oxidation treatment (step S3). [Figure 7] 4A and 4B are diagrams illustrating an example of the dependence of the etch rate on the etching step conditions in this embodiment, where FIG. 4A shows the dependence of the etch rate on the Cl2 processing time, and FIG. 4B shows the dependence of the etch rate on the bias power of the Cl2 processing. [Figure 8] FIG. 13 is a graph showing the dependence of the etching amount on the number of cycles when etching is performed using this embodiment. [Figure 9] FIG. 4 is an explanatory diagram of an example of a protective film removing step in the present embodiment. [Figure 10] FIG. 13 is a diagram showing another example of a pattern etched using the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. In all drawings, components having the same functions are denoted by the same reference numerals, and repeated description thereof will be omitted. EXAMPLES

[0016] The etching apparatus 30 according to this embodiment forms a protective film containing carbon (C) on the sidewall surface of a fine pattern of wiring material containing Mo (molybdenum) or Ru (ruthenium) formed on a wafer, which is a semiconductor substrate made of single crystal silicon, placed on a stage, and etches and removes the Mo film or Ru film, which is the material to be etched at the bottom of the pattern. After etching, the protective film remaining on the pattern, the oxidized components on Mo or Ru, and residues such as reaction products by etching are removed by plasma. In this embodiment, Mo or Ru is described as the material to be etched, but the same process as this embodiment can be carried out with a molybdenum-containing material (or a molybdenum-containing film) or a ruthenium-containing material (or a ruthenium-containing film).

[0017] 3 shows an overall configuration of an example of the plasma processing apparatus 30 used in this embodiment. The etching apparatus 30 as the plasma processing apparatus 30 includes a processing chamber 31, a wafer stage 32 on which a wafer is placed, a gas supply unit 33, a bias power supply 41, a high frequency application unit 42, an apparatus control unit 43, and the like. The apparatus control unit 43 includes functional blocks such as an optical system control unit, a gas control unit 44, an exhaust system control unit 45, a high frequency control unit 46, a bias control unit 47, a protective film forming process control unit 48, a determination unit 49, a memory unit 51, and a clock (not shown). Each of the functional blocks constituting the apparatus control unit 43 can be realized by one personal computer (PC). The apparatus control unit 43 includes a determination unit 49 and a database storage unit 50, and can determine whether the desired processing has been completed by the determination unit 49 by referring to the database 50, a signal sent from the optical system control unit.

[0018] The etching apparatus 30 is provided with a wafer stage 32 disposed within a processing chamber 31, and a gas supply unit 33 equipped with a gas cylinder and a valve, and based on a control signal 56 from the apparatus control unit 43, an etching gas 34, a protective film forming gas 35, a film quality control gas 36, an etching gas 37, and a protective film removal gas 38 are each supplied to the processing chamber 31 according to the processing step.

[0019] The processing gas supplied to the processing chamber 31 is decomposed into plasma 57 in the processing chamber 31 by high frequency power 53 applied to the high frequency application unit 42 from a high frequency power source 54 controlled by the device control unit 43. The pressure in the processing chamber 31 can be kept constant by a variable conductance valve and a vacuum pump (not shown) connected to the processing chamber 31 while a predetermined flow rate of processing gas is being flowed. The radicals generated by the decomposition into plasma 57 in the processing chamber 31 diffuse within the processing chamber 31 and are irradiated onto the surface of the wafer 100 placed on the wafer stage 32. The ions generated by the plasma 57 are accelerated by a bias voltage 55 applied to the wafer stage 32 from a bias power source 41 controlled by a bias control unit 47, and are irradiated onto the surface of the wafer 100.

[0020] The processed state of the wafer 100 can be determined by the determination unit 49 by acquiring the spectrum of light emitted from a light source (not shown) and reflected by the wafer 100, or the spectrum of light generated by the plasma 57. In the control unit 43, the reflection spectrum and the emission spectrum are stored in advance as a database 50 as reference data, and the state is determined by comparing the reflection spectrum and the emission spectrum with the reference data. In other words, the plasma processing device 30 has a function for observing the pattern shape (a light source, a determination unit 49 for determining the spectrum of light reflected by the wafer 100 or the spectrum of light generated by the plasma 57, and the reflection spectrum and the emission spectrum are stored in advance as reference data in the database 50, etc.), and is configured to adjust process conditions such as etching conditions (substrate temperature, flow rate of gas used, bias voltage, processing time such as etching time (oxidation time)) so as to obtain a desired pattern shape and pattern dimensions in the first step to the fourth step described later.

[0021] As an example of the etching method of this embodiment, a method of forming a protective film containing carbon (C) selectively on the material of a wiring material pattern containing Mo or Ru in the processing chamber 31, and then modifying the protective film containing carbon (C) to ensure etching resistance, and a method of processing the material to be etched such as Mo or Ru with a high selectivity using the modified protective film as a mask will be described.

[0022] The etching apparatus 30 according to this embodiment forms a protective film containing carbon (C) on the sidewall surface of a fine pattern of wiring material containing Mo or Ru formed on a wafer 100, and etches and removes Mo or Ru, which is the material to be etched at the bottom of the pattern, with plasma containing halogen. Furthermore, after etching, the protective film remaining on the pattern, oxidized components on Mo or Ru, and residues such as reaction products (altered layers) caused by etching are removed by irradiating plasma containing hydrogen (H).

[0023] FIG. 1 is a diagram showing an example of a process flow of the plasma processing method of this embodiment. FIG. 4 is an example of a pattern cross-sectional view explaining the process flow of the plasma method of this embodiment. In this embodiment, as shown in FIG. 4(a), a method of vertically processing a material 102 to be etched containing Mo or Ru formed on a surface of a substrate 101 using a mask pattern 103 as a mask will be explained based on the flow of FIG. 1. In FIG. 4, the substrate 101 corresponds to a wafer 100. In this embodiment, as an example, a case where the material of the mask pattern 103 is a silicon nitride film (SiN) and the material to be etched (pattern to be etched) 102 is Mo will be described. The material of the mask pattern 103 may be silicon oxide film (SiO2), silicon nitride film (SiN), silicon carbide (SiC: silicon carbide), etc., materials containing oxygen (O), nitrogen (N), and carbon (C) other than Si, materials containing titanium (Ti) such as titanium nitride (TiN: titanium nitride) and titanium dioxide (TiO2), materials containing aluminum (Al) or tantalum (Ta) such as aluminum oxide (Al2O3) and tantalum nitride (TaN), and materials containing carbon (C) can also be used in the same manner.

[0024] First, the wafer 100 is introduced onto the wafer stage 32 in the processing chamber 31, and a process of etching the material 102 to be etched with respect to the pattern formed on the wafer 100 is started (step S1: etching start process, first process). Based on a control signal 56 from the device control unit 43, the etching gas 34 is supplied to the processing chamber 31 at a predetermined flow rate. The supplied etching gas 34 becomes plasma 57 by the high frequency power 53 applied to the high frequency application unit 42, and generates radicals and ions that etch the material 102 to be etched. The radicals and ions generated by the plasma 57 reach the surface of the wafer 100, and as shown in FIG. 4(b), etching of the material 102 to be etched containing Mo or Ru is started using the mask pattern 103 as a mask. For example, chlorine gas (Cl2) is used as the etching gas 34. 、 A mixed gas of halogen gas such as hydrogen bromide gas (HBr), nitrogen trifluoride gas (NF3), sulfur hexafluoride gas (SF6), and O2 gas can be used. Alternatively, a fluorocarbon gas such as tetrafluoromethane gas (CF4), trifluoromethane gas (CHF3), or a mixed gas of hydrofluorocarbon gas and O2 gas can be used as the etching gas 34. Ions generated from the etching gas 34 are accelerated by a bias voltage 55 applied to the wafer stage 32 from a bias power supply 41 controlled by a bias control unit 47, and are irradiated onto the surface of the wafer 100.

[0025] Here, the etching in step S1 must be stopped before etching progresses toward the sidewall of the material 102 to be etched. It is desirable to obtain optimal values ​​for the etching time, bias voltage, and substrate temperature in step S1 in advance, but the determination unit 49 may determine the pattern dimensions and depth of the pattern of the grooves (recesses) formed by etching the material 102 to be etched by obtaining the spectrum of light emitted from a light source installed in the etching device 30 and reflected by the wafer 100, or the reflection spectrum of light generated by the plasma 57. Here, the horizontal direction is a direction horizontal to the surface of the wafer 100 (or the substrate 101), and the vertical direction is a direction perpendicular to the horizontal direction and perpendicular to the surface of the wafer 100 (or the substrate 101). The pattern dimensions refer to the horizontal interval of the grooves (recesses), and the pattern depth refers to the vertical depth of the grooves (recesses). When the pattern dimensions of the groove (recess) pattern of the material 102 to be etched are not within a predetermined range, for example, when the pattern dimensions are larger than the predetermined range, the pattern dimensions can be reduced to fall within the predetermined range by increasing the substrate temperature and etching. When the pattern dimensions are smaller than the predetermined size, the pattern dimensions can be increased to fall within the predetermined range by decreasing the substrate temperature and etching. When the dimensions of the initial mask pattern 103 have a distribution within the surface of the wafer 100, a groove (recess) pattern of uniform dimensions can be formed by changing the substrate temperature depending on the position within the wafer stage 32 and etching so that the pattern dimensions of the groove (recess) pattern formed by etching are within a predetermined range and are uniform.

[0026] Next, before the etching in the direction of the sidewall of the material 102 to be etched in the etching in step S1 progresses, a protective film 105 containing carbon (C) is formed on the surface including the pattern sidewall of the groove (recess) pattern of the material 102 to be etched (step S2: C-containing protective film forming process, second process) as shown in FIG. 4(c). Based on a control signal from the protective film forming process control unit 48, the protective film forming gas 35 is supplied to the processing chamber 31 at a predetermined flow rate, and becomes plasma 57 by the high frequency power 53 applied to the high frequency application unit 42, generating radicals and ions. The radicals and ions generated from the protective film forming gas 35 have the property of bonding with the material of the mask pattern 103 and the material 102 to be etched, or adhering thereto and depositing thereon, and the radicals and ions generated by the plasma 57 reach the surface of the wafer 100, and form a protective film 105 containing C on the upper surface of the mask pattern 103 and the pattern sidewall (sidewall surface) of the material 102 to be etched. In the protective film forming process control section 48, the flow rate of the protective film forming gas 35, the high frequency power 53 applied to the high frequency application section 42, the substrate temperature, the plasma irradiation time, etc. are set and adjusted, so that the thickness and quality of the protective film 105 can be controlled. For example, methane gas (CH4) is used as the protective film forming gas 35. 、 Methane tetrafluoride gas (CF4) 、 Trifluoromethane gas (CHF3) 、 Fluoromethane gas (CH3F) 、 Perfluorocyclobutane gas (C4F8), carbon dioxide gas (CO2) 、 Gases containing carbon (C) such as carbon monoxide gas (CO), or gases containing C and argon gas (Ar), helium gas (He), or O2 gas 、 CO2 gas 、 CO gas, nitrogen gas (N2) 、A mixed gas such as hydrogen gas (H2) can be used. The thickness of the protective film 105 can be adjusted by the plasma irradiation time, the gas flow rate of the protective film forming gas 35, the substrate temperature, and the like. Alternatively, the high frequency power 53 applied to the high frequency application unit 42 can be used to adjust the degree of dissociation of the plasma, thereby adjusting the reactivity of the generated radicals and ions with the material surface, thereby adjusting the thickness of the protective film 105. After the protective film 105 is formed, Ar gas, He gas, N2 gas, etc. are further added. 、 The shape of the protective film 105 may be smoothed by irradiating the groove (recess) pattern with plasma generated by introducing a gas such as H2 gas, thereby reducing the roughness of the groove (recess) pattern and the roughness of the protective film surface.

[0027] After forming the C-containing protective film 105 in step S2, an oxidation treatment is carried out (step S3: oxidation treatment step, third step) to remove unnecessary C-containing protective film 105 formed on the pattern bottom (or pattern bottom) of the groove (recess) and oxidize the Mo surface of the etched region 102 on the pattern bottom, as shown in Fig. 4(d). After oxidation of Mo on the pattern bottom, a halogen-containing plasma treatment is carried out in the next step S4, whereby the oxidized Mo (Mo oxide film) 106 is selectively etched, promoting the etching of Mo and enabling the etching of Mo on the pattern bottom to be well controlled.

[0028] First, based on a control signal 56 from the device control unit 43, the film quality control gas 36 is supplied to the processing chamber 31 at a predetermined flow rate. As the film quality control gas 36, a mixed gas of a gas containing oxygen (O), such as oxygen gas (O2), carbon dioxide gas (CO2), sulfur dioxide gas (SO2), and a rare gas, such as Ar and He, is supplied to the processing chamber 31. The supplied gas is turned into plasma by a high frequency power 53 applied to the high frequency application unit 42, and is decomposed into radicals, ions, etc., and is irradiated onto the surface of the wafer 100. Here, FIG. 5 shows an explanatory diagram of an example of a method for removing a protective film in the oxidation processing step (S3). Ions 107 such as Ar generated from the film quality control gas 36 are accelerated by a bias voltage 55 applied to the wafer stage 32 from the bias power supply 41 controlled by the bias control unit 47, and are irradiated onto the surface of the wafer 100. As an example, the protective film 105 is formed to the same thickness on the upper surface and sidewalls of the mask 103, and on the bottom surface and sidewalls of the groove (recess) of the material 102 to be etched. Carbon (C) in the protective film 105 reacts with oxygen radicals 108 generated from the film quality control gas 36 to generate CO2 and volatilize. At this time, if the ions 107 have energy capable of passing through the protective film 105 (1052) on the pattern bottom surface 120 of the groove (recess), the protective film 105 (1052) containing C reacts with the oxygen radicals 108 quickly, and the protective film 105 (1052) on the pattern bottom surface 120 can be removed. Furthermore, if the ions 107 have enough energy to pass through the protective film 105 (1052) on the bottom surface 120 of the pattern, the oxygen radicals 108 reach Mo (1022) of the material to be etched 102 below the protective film 105 (1052), and the Mo (1022) below the protective film 105 (1052) is easily oxidized (oxidized Mo (Mo oxide film) 106 in FIG. 4(d)). On the other hand, when ions 107 are irradiated onto the pattern sidewall 125 of the groove (recess) in the material 102 to be etched, the ions 107 are irradiated onto the protective film 105 (1055) deposited on the pattern sidewall 125 at a low incident angle, so that the ions 107 can only penetrate up to the surface region 1251 of the protective film 105 (1055). As a result, it takes more time to remove the protective film 105 (1055) on the pattern sidewall 125 of the material 102 to be etched than it takes to remove the protective film 105 (1052) on the pattern bottom surface 120.In addition, the protective film 105 (1055) on the pattern sidewall 125 can prevent the pattern sidewall 125 of the material 102 to be etched from being oxidized. In other words, it is preferable to apply a bias voltage 55 capable of irradiating ions with an energy that passes through the protective film 1052 formed on the pattern bottom 120 but does not pass through the protective film 1055 on the pattern sidewall 125 to the wafer stage 32 from the bias power supply 41 controlled by the bias control unit 47. Therefore, by adjusting the energy of the ions generated from the film quality control gas 36, the protective film 105 (1052) on the pattern bottom surface 120 can be removed while leaving the protective film 105 (1055) on the pattern sidewall 125, and the material 102 (1022) to be etched on the pattern bottom surface 120 can be oxidized.

[0029] Once the protective film 105 (1052) on the bottom surface 120 of the pattern has been removed, the oxide film (oxidized Mo (Mo oxide film) 106 in FIG. 4(d)) of the material to be etched 102 (1022) formed on the bottom surface 120 of the pattern is etched using a plasma containing halogen (Step S4: Etching process, fourth process).

[0030] First, based on a control signal 56 from the device control unit 43, the etching gas 37 is supplied to the processing chamber 31 at a predetermined flow rate. As the etching gas 37, a mixed gas containing halogens such as Cl2, HBr, CF4, CHF3, NF3, and SF6, fluorocarbon, and hydrofluorocarbon gas is supplied to the processing chamber 31. The supplied gas is turned into plasma by the high-frequency power 53 applied to the high-frequency application unit 42, decomposed into radicals, ions, and the like, and is irradiated onto the surface of the wafer 100, and as shown in FIG. 4(e), the oxidized components (Mo oxide film 106: FIG. 4(d)) of the oxidized etched material 102 (1022) on the pattern bottom surface 120 are preferentially etched. By accelerating the ions generated from the etching gas 37 by the bias voltage 55 applied to the wafer stage 32 from the bias power supply 41 controlled by the bias control unit 47, the oxidized etched material 102 (Mo oxide film 106: FIG. 4(d)) on the pattern bottom surface 120 can be etched more efficiently. On the other hand, since the etching of the material 102 to be etched on the pattern sidewall 125 is suppressed by the C-containing protective film 105, the lateral etching of the material 102 to be etched on the pattern sidewall 125 is suppressed, and the material 102 to be etched on the pattern bottom surface 120 can be etched in the vertical direction.

[0031] FIG. 6 shows an explanatory diagram of the oxidation treatment step (S3) when etching is performed by forming a protective film (step S2), performing an oxidation treatment (step S3), and performing etching (step S4). FIG. 6(a) shows the oxidation treatment time dependency of the etch rate. 112 shows the oxidation treatment time dependency of the etch rate when the C-containing protective film 105 is not formed on the material to be etched 102, and 113 shows the oxidation treatment time dependency of the etch rate when the C-containing protective film 105 is formed on the material to be etched 102. When the C-containing protective film 105 is not formed, the etching rate increases rapidly when the oxidation treatment (step S3) is performed, and is saturated at a certain etching rate (ER1). As an example, when Mo is oxidized at a pressure of 0.2 Pa, the etching rate is saturated at 4 nm / cycle. It was found that when the C-containing protective film 105 is formed on the material to be etched 102, oxidation for a certain oxidation treatment time (T) or more is required to be etched. This indicates that oxidation is suppressed by the C-containing protective film 105, and that time is required to remove the C-containing protective film 105 by oxidation. Even when the C-containing protective film 105 is formed, if the oxidation treatment time is extended, the etch rate (ER1) becomes saturated at approximately the same rate as when the C-containing protective film 105 is not formed, indicating that the C-containing protective film 105 is removed by oxidation.

[0032] Figure 6(b) shows the bias power dependence of the saturated etch rate (ER1) in the oxidation process (step S3). Mo, which is the material 102 to be etched, is a material that is easily oxidized. When the oxidation process (step S3) is performed by plasma, the thickness of the Mo oxide film does not depend greatly on the bias power. Therefore, it was found that the saturated etch rate hardly depends on the bias power in the oxidation process (step S3). For example, even if the O2 process time is increased from 1 second to 10 seconds, the etch rate remains constant at about 4 nm / cycle, and even if the bias power in the O2 process is increased from 0 W to 50 W, the etch rate remains almost constant at about 4 nm / cycle.

[0033] FIG. 6(c) shows the bias power dependency of the oxidation process time (T) until etching starts when the C-containing protective film 105 is formed (step S3). It can be seen that the time to remove the protective film 105 depends greatly on the bias power of the oxidation process (step S3), that is, the ion energy. When etching a line pattern as shown in FIG. 4, ions are incident on the protective film 105 (1052) on the pattern bottom surface 120 from a vertical direction, but the ions are incident on the protective film 105 (1055) on the pattern sidewall 125 at a low angle, so the energy in the vertical direction to the protective film 105 (1055) on the pattern sidewall 125 is small, and the time (Tsw) required to remove the protective film 105 (1055) on the pattern sidewall 125 is longer than the time (Tbtm) required to remove the protective film 105 (1052) on the pattern bottom surface 120 (Tsw>Tbtm). Therefore, by setting the oxidation treatment time of the oxidation treatment (step S3) between Tbtm and Tsw, the protective film 105 (1052) on the pattern bottom surface 120 can be removed while leaving the protective film 105 (1055) on the pattern sidewalls 125. By removing the protective film 105 (1052) on the pattern bottom surface 120, the etched material 102 (1022) only on the pattern bottom surface 120 can be oxidized.

[0034] FIG. 7 shows an example of the etching step condition dependency of the etch rate in this embodiment. In the case where Cl2 was used as the halogen gas in the etching step (S4), FIG. 7(a) shows the Cl2 processing time dependency of the etch rate, and FIG. 7(b) shows the Cl2 processing bias power dependency of the etch rate. As the Cl2 processing time became longer and as the Cl2 processing bias power increased, the etch rate tended to increase little by little. For example, when the Cl2 processing time was increased from 3 seconds to 20 seconds, the etch rate increased from 3 nm / cycle to 6 nm / cycle, and when the Cl2 processing bias power was increased from 0 W to 50 W, the etch rate increased from 3 nm / cycle to 5-6 nm / cycle.

[0035] Here, in the protective film forming step (S2) of forming the C-containing protective film 105 on the pattern sidewall 125 and the oxidation treatment step (S3) of oxidizing the C-containing protective film 105 on the pattern bottom surface (bottom) 120, the protective film 105 below the pattern sidewall 125 is oxidized and removed, so that the lower part of the pattern sidewall 125 is etched in the lateral direction, and the pattern dimensions can be made uniform within the surface of the wafer 100. It is desirable to obtain optimal values ​​for the etching time (oxidation time), bias voltage, and substrate temperature in the oxidation treatment step S3 in advance, but the pattern dimensions and depth may be determined by the determination unit 49 by obtaining the spectrum of light emitted from a light source installed in the etching device 30 and reflected by the wafer 100, or the reflection spectrum of light generated by the plasma 57, and the pattern shape may be observed. If the pattern dimensions are not within a predetermined range, for example, if the pattern dimensions are larger than the predetermined dimensions, the substrate temperature is increased and the oxidation treatment step (S3) and the etching step (S4) are performed to reduce the pattern dimensions to fall within the predetermined range. For example, when the substrate temperature is 10° C., the etch rate is 2 nm / cycle, but when the substrate temperature is increased to 80° C., the etch rate increases to 5 nm / cycle. When the pattern dimension is smaller than the predetermined dimension, the substrate temperature is lowered and the oxidation step (S3) and the etching step (S4) are performed, so that the pattern dimension can be increased to fall within the predetermined range. Alternatively, the pattern dimension can be reduced to fall within the predetermined range by increasing the substrate temperature and thinning the thickness of the protective film 105 in the protective film forming step (S2). On the other hand, when the pattern dimension is increased to fall within the predetermined range, this can be achieved by decreasing the substrate temperature and thickening the protective film 105 in the protective film forming step (S2). By changing the substrate temperature within the wafer surface and performing etching, the pattern dimension can be precisely adjusted. That is, in the oxidation step (S3), the in-plane temperature distribution of the wafer stage 32 is adjusted to adjust the substrate temperature of the wafer 100, and the in-plane pattern dimension on the surface of the wafer 100 can be made uniform.Alternatively, it is preferable to provide a step of observing the pattern shape and adjusting process conditions such as the etching conditions of the etching start step (S1), the protective film formation step (S2), the oxidation treatment step (S3), and the etching step (S4) (substrate temperature, flow rate of the gas used, bias voltage, processing time such as etching time (oxidation time)) so as to obtain the desired pattern dimensions.

[0036] While performing the etching process (S4), the thickness, pattern dimensions, and etching depth of the protective film 105 are measured by an optical system, and one cycle of the protective film forming step (S2), the oxidation treatment step (S3), and the etching step (S4) is repeated a predetermined number of times until the pattern depth of the material to be etched 102 on the wafer 100 is etched to the desired etching depth, and the etching is terminated (step S5) when the predetermined number of etching processes or the desired etching depth is reached (Yes). Here, the cyclic process refers to a process in which one cycle of the protective film forming step (S2), the oxidation treatment step (S3), and the etching step (S4) is repeated a predetermined number of times. FIG. 8 shows the cycle number dependency of the etching amount when the cyclic process shown in this embodiment is used. It was confirmed that a certain amount of etching depth is progressed per cycle.

[0037] As shown in FIG. 4(f), after etching to a predetermined depth, the C-containing protective film 105 is removed (step S6: protective film and residue removing step, fifth step). FIG. 9 shows a schematic diagram of a pattern cross section after etching to a predetermined depth. On the pattern of the material 102 to be etched, the C-containing protective film 105, the oxide film 106 of the oxidized material 102 to be etched, and the etching residue 111 are formed. For example, when the material 102 to be etched is a wiring material, the C-containing protective film 105, the oxide film 106 of the oxidized material 102 to be etched, and the etching residue 111 remaining on the material 102 to be etched need to be removed after etching because they may be mixed as impurities into the wiring material to increase the wiring resistance or cause disconnection. In addition, in fine wiring and the like, since the wiring width and the pitch between wirings are small (narrow), it was necessary to remove the C-containing protective film 105, the oxide film 106 of the oxidized material to be etched 102, and the etching residue 111 without removing the unaltered material to be etched 102. Furthermore, since the roughness of the sidewall 125 of the material to be etched 102 after removing the C-containing protective film 105, the oxide film 106 of the oxidized material to be etched 102, and the etching residue 111 increases the wiring resistance, it was necessary to suppress the roughness and remove them.

[0038] In the protective film and residue removal step (S6), first, the device control unit 43 controls the gas supply unit 33 to supply the protective film removal gas 38 to the processing chamber 31 at a predetermined flow rate. In a state where the protective film removal gas 38 is supplied and the inside of the processing chamber 31 is at a predetermined pressure, the device control unit 43 controls the high frequency power supply 54 to apply high frequency power 53 to the high frequency application unit 42 to generate plasma by the protective film removal gas 38 inside the processing chamber 31. The protective film removal gas 38 becomes plasma and generates radicals 109 and ions 110 that remove the protective film 105 on the material to be etched 102, the oxide film 106 of the oxidized material to be etched 102, and the etching residue 111. The etching residue 111 can be called an altered layer. For example, a mixed gas containing H2 gas can be used as the protective film removal gas 38. Alternatively, a mixed gas of H2 gas and N2 or the like can be used. The C-containing protective film 105 reacts with the H radicals 109 and the H ions 110 to generate CH-based reaction products and can be removed. At this time, the material to be etched 102 under the protective film 105 does not react with H, so the protective film 105 can be removed without chipping the material to be etched 102. The oxide film 106 of the oxidized material to be etched 102 can be reduced by the hydrogen radicals 109 and the hydrogen ions 110 to generate H2O. The etching residue 111 includes, for example, reaction products of the C-containing protective film 105 and halogen ions and halogen radicals. Such reaction products of carbon (C) and halogen can be volatilized and removed by the hydrogen radicals 109 and the hydrogen ions 110. In this way, the processed material to be etched 102 can be removed without chipping. In addition, this removal step S6 may be performed after removing the mask material 103.

[0039] FIG. 10 shows an example of another embodiment of the pattern etched in this embodiment. Patterns with different dimensions (spacing) in the horizontal direction are formed on the surface of the same wafer 100 (substrate 101) as mask patterns 103, and the material 102 to be etched is processed with different pattern dimensions (spacing). When etching patterns 114 with different processing dimensions formed on the same wafer 100, the etching depth may differ depending on the pattern dimensions. However, in this embodiment, an oxide film 106 with the same thickness is formed in the oxidation step (S3) even at the bottom of the patterns with different dimensions, and the oxide film 106 is etched in the etching step (S4), so that the bottom of the patterns with different dimensions (spacing) in the horizontal direction can be processed to the same etching depth.

[0040] In this manner, the C-containing protective film 105 is formed on the pattern sidewall 125 (S2), the C-containing protective film 105 (1052) on the pattern bottom surface (bottom) 120 is oxidized (S3), and the oxide film 106 of the etched material 102 on the pattern bottom 120 is etched (S4). This makes it possible to suppress lateral etching of the pattern and process the pattern in the vertical direction. In addition, by oxidizing and removing the unnecessary C-containing protective film 105 attached to the pattern bottom 120 and oxidizing the molybdenum or ruthenium that is the etched material 102 on the pattern bottom 120, uniform processing can be performed within the surface of the wafer 100. Furthermore, after etching to a desired depth, the C-containing protective film 105 and the etching residue 111 on the pattern sidewall 125 are removed by treating with plasma containing hydrogen (step S6) without progressing the etching of molybdenum or ruthenium on the sidewall 125 of the etched material 102. This makes it possible to perform patterning of the material to be etched 102 without causing defects or deteriorating electrical characteristics such as wiring resistance.

[0041] In addition, in this embodiment, the case where a pattern shape perpendicular to the substrate 101 has been mainly described, however, it is also possible to form a pattern having an inverse tapered shape by forming a C-containing protective film 105 on the pattern sidewall 125 (S2), and then oxidizing and removing the protective film 105 below the pattern sidewall 125 in the oxidation treatment step (S3) of oxidizing the pattern bottom 120, thereby etching the lower part of the pattern sidewall 125 laterally.

[0042] Although the present disclosure has been specifically described based on the embodiments, it goes without saying that the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the gist of the disclosure. For example, the above embodiments have been described in detail to clearly explain the present disclosure, and are not necessarily limited to those having all of the configurations described. In addition, it is possible to add, delete, or replace part of the configuration of each embodiment with other configurations. [Explanation of symbols]

[0043] 30: Etching device, 31: Processing chamber, 32: Wafer stage, 33: Gas supply unit, 34: Etching gas, 35: Protective film forming gas, 36: Film quality control gas, 37: Etching gas, 38: Protective film removal gas, 41: Bias power supply, 42: High frequency application unit, 43: Equipment control unit, 44: Gas control unit, 45: Exhaust system control unit, 46: High frequency control unit, 47: Bias control unit, 48: Protective film forming process control unit, 49: Determination unit, 50: Database, 51: Memory unit, 52: Clock, 53: High frequency power, 54: High frequency power supply, 55: Bias voltage, 56: Control signal, 57: Plasma, 100: Wafer, 101: Substrate, 102 : material to be etched, 103: mask, 104: SiO2 protective film, 105: C-containing protective film, 106: oxide film, 107: ions, 108: oxygen radicals, 109: hydrogen radicals, 110: hydrogen ions, 111: residues, 112: oxidation treatment time dependence of etching rate when no protective film is present, 113: oxidation treatment time dependence of etching rate when a protective film is formed, 114: patterns of different dimensions, ER1: saturated etching rate, T: oxidation time until etching starts, Tsw: oxygen treatment time required for sidewall etching, Tbtm: oxygen treatment time required for bottom of pattern etching

Claims

1. A first step of forming a pattern on a molybdenum-containing or ruthenium-containing film using a plasma generated by a mixture of an oxygen-containing gas and a halogen-containing gas; a second step of forming a protective film on the pattern using plasma generated by a carbon-containing gas after the first step; a third step of oxidizing the molybdenum-containing film or the ruthenium-containing film at the bottom of the pattern using plasma generated by an oxygen-containing gas after the second step; and a fourth step of etching the oxidized molybdenum-containing film or the oxidized ruthenium-containing film using plasma generated by a halogen-containing gas after the third step, A plasma processing method comprising repeating the second to fourth steps until a predetermined pattern depth is achieved.

2. 2. The plasma processing method according to claim 1, The plasma processing method further comprises a fifth step of removing, after the fourth step, the altered layer formed on the surface of the molybdenum-containing film or the altered layer formed on the surface of the ruthenium-containing film and the protective film by using plasma generated by a hydrogen-containing gas.

3. 2. The plasma processing method according to claim 1, The plasma processing method, wherein the halogen-containing gas is chlorine gas (Cl2), hydrogen bromide gas (HBr), nitrogen trifluoride gas (NF3) or sulfur hexafluoride gas (SF6).

4. 2. The plasma processing method according to claim 1, The plasma processing method is characterized in that the halogen-containing gas is tetrafluoromethane gas (CF4) or trifluoromethane gas (CHF3).

5. 2. The plasma processing method according to claim 1, The plasma processing method is characterized in that the carbon-containing gas is methane gas (CH4), tetrafluoromethane gas (CF4), trifluoromethane gas (CHF3), fluoromethane gas (CH3F), perfluorocyclobutane gas (C4F8), carbon monoxide gas (CO), or carbon dioxide gas (CO2).

6. 3. The plasma processing method according to claim 1, The plasma processing method further comprises, after the second step, a step of reducing roughness of the protective film using plasma generated from argon gas (Ar), helium gas (He), nitrogen gas (N2), and hydrogen gas (H2).

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