JP5130652B2 - Metal film etching method and semiconductor device manufacturing method - Google Patents

Description

  The present invention relates to a method for etching a metal film, particularly a metal film for etching a refractory metal thin film, and a method for manufacturing a semiconductor device using the same.

2. Description of the Related Art With the recent progress in technology for higher integration and higher speed in semiconductor devices, the miniaturization of channels such as gate electrodes, source / drains, and the like constituting the semiconductor devices has been promoted. Among these miniaturizations, there is a problem that when the gate insulating film constituting the gate electrode is made thinner, the leakage current due to the tunnel current becomes larger. In order to suppress this problem, metal oxides including hafnium oxide (HfO ₂ ), zirconium oxide (ZrO ₂ ), lanthanum oxide (LaO ₂ ), etc. have a high dielectric constant, which is generally called high-k. Development of a gate insulating film that satisfies the physical and electrical characteristics while being a thin oxide film by using a dielectric constant material for the gate insulating film is underway.
For example, in Patent Document 1, the interface characteristics between a polycrystalline Si film and a high dielectric constant insulating film are improved by applying simple means, and the threshold voltage in a MOS-FET using a high dielectric constant gate insulating film is shifted. A method of manufacturing a semiconductor device that prevents this is disclosed.

However, in Patent Document 1, by thinning the gate insulating film, the depletion layer formed in the Si substrate by applying a voltage to the gate insulating film can be easily controlled, and the short channel effect is suppressed. However, when the gate electrode of the semiconductor device is formed of impurity-doped polysilicon as in the prior art, the electric field applied to the gate electrode becomes relatively strong due to the thinning of the gate insulating film, and the gate electrode In addition, a depletion layer is formed, and the on-state current of the transistor is reduced. In addition, there is a problem that the gate insulating film made of a high dielectric constant material reacts with the polysilicon gate electrode. Therefore, in order to cope with the depletion of the gate electrode due to polysilicon, it has been proposed to form the gate electrode with a metal gate electrode made of a metal material.
As a metal material used for this metal gate electrode, for example, Al has a low melting point. Therefore, when heat treatment is performed for the purpose of activating the source and drain, disconnection of the gate electrode, diffusion of Al atoms into the peripheral region, etc. Problems occur. Further, a metal having a high melting point ratio such as W, Mo, Ti or the like is used. However, these metals have a problem that their characteristics change due to oxidation. Further, W and the like are disadvantageous in that they are dissolved when acid cleaning is performed and the cleaning resistance is low.
Therefore, as a gate electrode made of metal other than polysilicon, W or the like used on the gate oxide film of this high dielectric constant material, for example, in Patent Document 2, a gate electrode having a polymetal structure formed on a gate insulating film A method of manufacturing a semiconductor device is disclosed that prevents damage such as penetration through the gate insulating film when forming the film by dry etching.
Further, Patent Document 3 discloses a semiconductor device that can prevent high-dielectric-constant gate insulating film scraping and semiconductor substrate digging, and realize high-precision gate electrode processing with little dimensional conversion difference, and a manufacturing method thereof. Has been.
However, such a conventional technique has a problem that it is insufficient to etch only the gate electrode made of a refractory metal and protect the underlying gate insulating film.

JP 2006-086151 A JP 2004-031546 A JP 2005-285809 A

Therefore, the present invention has been made in view of the above-mentioned problems, and the problem is high-definition etching the metal film little by little without etching the thin film of the lower dielectric constant material that supports the metal film. It is to provide a method for etching a metal film.
Furthermore, a method for manufacturing a semiconductor device is provided in which a metal film to be a gate electrode is etched by increasing a selection ratio between a gate insulating film of a high dielectric constant material and a resist film provided when forming a gate electrode in the semiconductor device. It is to be.

In order to solve the above-described problems, the present invention applies an etching process to a metal film such as Ru, Ir, Pt and / or a metal film of these oxides by applying an ion or radical of a chlorine atom and an electric field such as a high-frequency bias. The first step of exposing and adsorbing without etching and the second step of etching the metal film in which chlorine atoms are adsorbed by oxygen ions or radicals, for example, chlorine atoms and / or Alternatively, the metal film etching method etches only the metal film without etching the oxide layer that is easily etched by oxygen atom plasma or the like.
Further, the present invention is an application of the method for producing a metal film, wherein the step of forming a gate electrode on the semiconductor substrate includes the step of forming chlorine atoms on the metal film formed on the oxide layer on the semiconductor substrate. A semiconductor device comprising: a first step of exposing and adsorbing a metal film without applying an electrical bias to ions or radicals; and a second step of etching by applying an electrical bias to ions or radicals containing oxygen. It is a manufacturing method. This semiconductor manufacturing method includes both the first step and the second step, so that a high dielectric constant material containing an oxide such as Hf, Zr, or La, an oxide of SiO ₂ , or Al ₂ O _{3 as} a base, In particular, the etching of the gate insulating material formed of HfO ₂ can be suppressed, and a metal such as Ru, Ir, Pt and these oxides as a metal film can be etched in one to several thin layers. By repeating this, the metal film is etched to a predetermined thickness.

In the metal film etching method of the present invention, the metal of Ru, Ir, Pt and the metal film of these oxides are highly precise for each layer without etching a layer of a high dielectric constant material provided in another lower layer. Etching can be performed.
In addition, the method of manufacturing a semiconductor device according to the present invention includes Ru, Ir, and Pt metals and oxides thereof without etching the gate insulating layer of a high dielectric constant material containing an oxide such as Hf, Zr, or La in the lower layer. By etching the gate electrode layer into a thin layer, a semiconductor device having a thin gate electrode can be manufactured.

The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.
The etching apparatus used for the metal film etching method of the present invention is not limited to any of the cathode coupling method, the floating method, and the anode coupling method, but the RIE cathode coupling method is preferable. In this RIE (Reactive Ion Etching (Reactive Ion Etching)) method, a high frequency is applied to the electrode of the sample stage and the opposite electrode is grounded, so that the ions are perpendicularly incident on the substrate. Etching.
FIG. 1 is a schematic view showing the configuration of an etching apparatus used in the metal film etching method of the present invention.
The etching apparatus 50 has a transparent glass window (not shown) in a part of the chamber 51 for reaction, and the reaction can be confirmed from the glass window by light or the like due to an internal reaction. In the chamber 51, a cathode-side planar electrode 52 for placing the object 60 to be etched and an opposing planar electrode 53 are arranged. The cathode-side planar electrode 52 is connected to a 13.56 MHz high-frequency power source 54, and the chamber 51 body is grounded. Further, an etching gas supply pipe 56 and an exhaust pipe 57 are connected to the chamber 51. A heating element 55 for heating is disposed on the planar electrode 52 on which the object to be etched 60 is placed.

FIG. 2 is a schematic view for explaining the metal film etching method of the present invention.
The reactive ion etching (RIE) method uses a reaction between ions and / or radicals in plasma generated by applying a high frequency bias and an object to be etched 60. By increasing the directionality of ions incident on the object to be etched 60 and using high energy plasma, the physical action of etching is enhanced and high anisotropy is obtained. However, in the conventional RIE method, the object 60 to be etched is inevitably damaged due to etching with high energy ions or the like. Therefore, in the present invention, the energy of ions or plasma to be etched is reduced to enable fine etching.
As shown in FIG. 2 (1), in the etching method for a metal film of the present invention, as a first step, using an etching gas containing chlorine element, Ru and exposed to chlorine such as plasma is adsorbed on the metal film 61. The d Tchingugasu, for _{example, CF 4, CHF 3, HBr} , BCl 3, Cl 2, Br 2, HCl, a halogen compound are preferred, such as CCl _4, in particular, chlorine is preferred. This is because chlorine plasma is highly chemically reactive and easily reacts with metals.
The metal at this time is preferably a high melting point noble metal. For example, Ru, Ir, Pt, etc. can be mentioned. If these precious metals are subjected to heat treatment in the manufacturing process of the semiconductor device, etc., oxidation due to heat can be suppressed. In particular, Ru, Ir, and Pt are preferable. Among these metals, Ru is particularly preferable. These metals do not oxidize Pt, Ir, and Ru, or oxides such as RuO ₂ , IrO ₂ , and PtO ₂ have conductivity even when oxidized. Further, since these have a large work function, it is possible to increase the Schottky barrier at the interface with the oxide film.

An etching gas containing chlorine element is supplied to the chamber 51 through the supply pipe 56, and a high frequency bias is applied by the high frequency power source 54. As a result, the etching gas is ionized to generate chlorine gas ions or radicals.
The chlorine ions or radicals are attracted to the object to be etched 60 and adsorbed on the surface thereof by being exposed without applying a bias between the planar electrodes 52 and 53. The adsorption is performed on one layer on the surface of the metal film 61. In chemisorption, chlorine ions or radicals react with the metal and adsorb only one layer . At this time, as shown in FIG. 2 (2), the metal and chlorine plasma react to form a secondary product (Ru—Cl). Although this secondary product is separated from the surface of the metal film 61, the vapor pressure is low, so that it does not leave the surface of the metal film 61 and exists on the surface of the metal film 61. This is the same when these noble metals form oxides. Therefore, in the first step, since no high frequency bias or the like is applied, only chlorine ions or radicals are adsorbed, and almost no etching is performed.

Next, as a second step, as shown in FIG. 2C, a high frequency bias is applied to the oxygen molecules O ₂ to form ions or radicals of oxygen atoms. The oxygen ions or radicals are applied to the surface of the metal film 61 on the object to be etched 60 by applying a constant speed with an electric field of high frequency bias, and etching is performed.
At this time, as shown in FIG. 2 (4), the etching is performed by causing oxygen ions or radicals to collide with the secondary product (Ru—Cl) in which the ruthenium metal Ru and the chlorine plasma react. The
This is because the secondary product obtained by the reaction between the metal and the chlorine plasma does not have enough energy to naturally evaporate and leave, so that it remains on the surface of the metal film. The accelerated oxygen plasma collides therewith to form a tertiary product (Ru—Cl—O), which is etched together with the secondary product (Ru—Cl) released by impact.
As described above, the secondary product remains on the surface of the metal film 61, but since it is separated from the surface of the metal film 61, even if the energy of the oxygen plasma is small, it can be detached and etched. The energy of the oxygen plasma at this time is preferably smaller than the energy that can be etched by separating the metal when it collides with the metal film 61 itself. Thus, the metal can be etched every thin layer or several thin layers.

At this time, an oxide layer 62 having a high dielectric constant, for example, which is easily etched with an etching gas containing chlorine and / or oxygen may be provided below the metal film 61. The insulating material having a high dielectric constant that is easily etched may include at least one metal oxide selected from Hf, La, and Zr, and further SiO ₂ and Al ₂ O ₃ . These insulating materials are materials having a relative dielectric constant higher than those of silicon oxide SiO ₂ and Al ₂ O ₃ alone, preferably a material having a relative dielectric constant of 10 or more, and a so-called high-k material is used. be able to. Since the oxide layer 62 containing the metal element has a high relative dielectric constant and good heat resistance, it contributes to reducing the size and improving the reliability of the MOS-FET.
However, the high dielectric constant material is easily etched when a mixed gas of chlorine and oxygen is used as an etching gas. In addition, in etching using a mixed gas as an etching gas, it is difficult to etch one or more thin layers, and the metal oxide layer 62 may be etched through the thin metal layer 61. In particular, when used in the semiconductor device 1 or the like, the thickness of the oxide layer 62 can be reduced by using high-k , which is usually several nanometers. Useless. Further, for example, when the oxide layer 62 has a high-k / SiO ₂ structure, the thickness of the SiO ₂ layer is 0.5 nm or less, which is less effective as a normal etching stop film, and the lower oxide layer. The etching of 62 cannot be prevented.
However, in the method for etching a metal film according to the present invention, the etching gas in the first first step is adsorbed to the metal film 61 because it moves relatively freely by being exposed without applying a high frequency bias. On the other hand, in the next second step, etching to the lower insulating layer can be suppressed with a low energy oxygen plasma by applying a weak high-frequency bias. With this high frequency bias, the energy of the oxygen plasma is set to 500 eV or less, preferably 200 eV or less. Thereby, the metal film 61 can be etched thinly.
As described above, the metal film etching method of the present invention enables fine processing by using both the etching gas and the applied high-frequency bias for each process.
Further, after the first step and the second step are finished, the remaining oxygen ions or plasma and secondary products are discharged, and then the previous etching step is repeated. Thus, by repeating this etching step, it is possible to control the thin film thickness of the metal film 61 to be etched.

Furthermore, in the method for manufacturing a semiconductor device according to the present invention, the gate electrode 12 having the metal film electrode 12A on the gate oxide film 12B made of a high dielectric constant material is formed on the semiconductor substrate 10. The step of forming the gate electrode 12 includes a first step of exposing and adsorbing chlorine atom ions or radicals to the metal film 21 and a second step of etching with oxygen atom ions or radicals.
FIG. 3 is a schematic view showing an embodiment of a method for manufacturing a semiconductor device of the present invention.
As shown in FIG. 3A, an element isolation region 11 is defined in the semiconductor substrate 10. As the semiconductor substrate 10, a silicon single crystal silicon substrate is used. Specifically, after forming a groove to be the element isolation region 11 in the semiconductor substrate 10 and depositing an insulator (SiO ₂ or the like) to a thickness to fill the groove, the semiconductor substrate 10 is formed by CMP (Chemical Mechanical Polishing) method. An STI (Shallow Trench Isolation) element isolation region 11 having a trench filled with an insulating material is formed thereon.
Next, as shown in FIG. 3B, an insulating layer 22 for the gate insulating film of the semiconductor substrate 10 is formed. After the natural oxide film formed on the surface of the semiconductor substrate 10 is removed, a high dielectric constant of about several nanometers in thickness is formed on the semiconductor substrate 10 as an insulating film 22 by a chemical vapor deposition method such as a CVD method or a solution method such as a sol-gel method. A thin film made of a material is formed. The insulating layer 22 is formed of a so - called high-k high dielectric constant material. As the high dielectric constant material, a material containing an oxide of at least one metal selected from Hf, La, and Zr is used. The gate insulating layer 12B formed of these oxides has high electrical insulation and dielectric constant, and can reduce the leakage current in the semiconductor device 1. Further, since the dielectric constant is high, the degree of integration of the semiconductor device 1 can be increased by thinning the gate insulating layer 12B in order to obtain a certain insulating property. Here, Hf silicate is deposited by MOCVD (Metal Organic Chemical Vapor Deposition) method to form, for example, a 4 nm gate insulating layer 12B.

The gate electrode layer 12A is formed of the metal film layer 21 made of Ru, Ir, Pt or an oxide thereof by a chemical vapor deposition method such as a CVD method or a solution method such as a sol-gel method. Here, ruthenium Ru is deposited to a thickness of 25 nm by the MOCVD method using Ru (EtCp) ₂ to form the Ru thin film layer 21 as a thin metal layer. Note that a layer made of another insulating material may be provided between the gate insulating layer 12B and the gate electrode layer 12A. For example, SiN is deposited under a predetermined temperature condition of, for example, about 680 ° C. in a gas system of SiH ₂ Cl ₂ (DCS; dichlorosilane) -NH ₃ (ammonia) by LPCVD (Low Pressure Chemical Vapor Deposition) method, For example, a 0.2 nm SiN film (silicon nitride film) may be formed. Further, a SiO ₂ film (silicon oxide film) is formed by oxidizing the surface of the SiN film (CVD-SiN) deposited thereon by CVD (Chemical Vapor Deposition) method in ozone at room temperature. be able to. Even if the surface of the SiN film (CVD-SiN) deposited by the CVD method is oxidized in oxygen at a predetermined temperature condition of, for example, about 600 ° C., a SiO ₂ film (silicon oxide film) is formed. good.

Next, as shown in FIG. 3 (3), a resist layer 20 is provided on the Ru thin film layer 21. Next, as shown in FIG. 3 (4), patterning is performed, and this resist pattern is used as an etching mask to form the gate electrode 12. At this time, the semiconductor substrate 10 is mounted on the etching apparatus 50, and the metal film layer (Ru thin film) 21 is etched to form the gate electrode 12A.
FIG. 4 is a schematic view for schematically explaining an etching step in the method for manufacturing a semiconductor device of the present invention. As shown in FIG. 4 (1), as a first step of the etching process, plasma is formed , chlorine ions or radicals are introduced , and chlorine ions or radicals are adsorbed on the Ru thin film layer 21 of the semiconductor substrate 10. For example, the etching conditions are set such that the pressure is in the range of 0.1 Pa to 10000 Pa, the substrate temperature is in the range of 600 to 900 ° C., and no high frequency bias is applied. At this time, as shown in FIG. 4B, chlorine ions or radicals on the Ru thin film layer 21 form Ru atoms and secondary products (Ru—Cl), but the vapor pressure is low, and the Ru thin film. Does not leave the surface of the layer 21.
4 (3), oxygen ions or radicals are introduced as the second step, and the etching conditions are, for example, a pressure of 0.1 Pa to 10000 Pa and a substrate temperature of 600 to 900 ° C. A high frequency bias is applied so as to apply a small energy of 200 to 500 eV to oxygen ions or radicals .
At this time, as shown in FIG. 4 (4), the secondary product (Ru—Cl) on the Ru thin film layer 21 is lightly impacted by the impact of oxygen ions or radicals , and the secondary product (Ru—Cl) on the Ru thin film layer 21 is applied to Release as secondary product (Ru-Cl) or tertiary product with oxygen (Ru-Cl-O). However, since the energy of oxygen ions or radicals is small, Ru atoms can be etched from the Ru thin film layer 21 little by little.
Further, the resist layer 20 is removed by oxygen ions or radicals . Resist removal by oxygen ions or radicals, resin for resist, which utilizes the fact that become carbon dioxide (CO ₂₎ and water (H 2 _O) by oxygen ions or radicals. However, in the method for manufacturing a semiconductor device according to the present invention, since the energy of oxygen ions or radicals is small, the amount of etching and removal of the resist layer 20 is small. For this reason, the selectivity of the Ru thin film layer 21 and the resist layer 20 can be increased.
However, at this time, the separated secondary product (Ru—Cl) or the like is deposited on the side surface of the gate electrode layer 12A where the Ru thin film layer 21 is etched to form the deposited layer 23. The deposited layer 23 suppresses the progress of etching due to oxygen ions or radicals, thereby enabling anisotropic etching.
Next, as shown in FIG. 4 (5), the deposited layer 23 is removed by oxygen ions or radicals , and the insulating layer 22 is removed by etching. Therefore, here, if excessive etching is performed to remove the deposited layer 23 on the side wall of the gate electrode layer 12A, the etching of the lower insulating layer 22 proceeds. Therefore, when etching the Ru thin film layer 21, uniformity of etching is required. If the etching of the Ru thin film layer 21 becomes nonuniform, the etching of the insulating layer 22 also becomes nonuniform, and the surface of the semiconductor substrate 10 is etched nonuniformly. Therefore, the lower insulating layer 22 can be uniformly etched by etching the Ru thin film layer 21 uniformly as in the present invention.

Next, as shown in FIG. 3 (5), n-type or p-type impurity element ions are implanted using the gate electrode 12 in the semiconductor substrate 10 as a self-aligned mask, and n-type or p-type is formed on both sides of the gate electrode 12. Forming a source extension region or a drain extension region. Further, an insulating film such as a SiO ₂ film is formed on the semiconductor substrate 10 so as to cover the gate electrode 12 by the CVD method, and this is etched back, whereby the sidewall insulating film 12C is formed on both side walls of the gate electrode 12. Form.
Further, as shown in FIG. 3 (6), ion implantation of an n-type or p-type impurity element is performed into the semiconductor substrate 10 using the gate electrode 12 and the sidewall insulating film 12C as a mask, and n outside the sidewall insulating film 12C. A source 14 and a drain 15 are respectively formed in a source or drain diffusion region of a p-type or p-type. Then, heat treatment (annealing) is performed to activate the impurities. Thereafter, the process proceeds to a process of forming a metal wiring, an interlayer insulating film, and a via hole, and a stacked semiconductor device is manufactured.

It is the schematic which shows the structure of the etching apparatus used for the etching method of the metal film of this invention. It is the schematic shown in order to demonstrate the etching method of the metal film of this invention. It is the schematic which shows embodiment of the manufacturing method of the semiconductor device of this invention. It is the schematic for demonstrating typically the etching process in the manufacturing method of the semiconductor device of this invention.

DESCRIPTION OF SYMBOLS 1 Semiconductor device 10 Semiconductor substrate 11 STI element isolation region 12 Gate 12A Gate electrode layer 12B Gate insulating layer 12C Side wall insulating film 14 Source 15 Drain 16 Channel region 20 Resist layer 21 Metal film (Ru thin film)
22 Insulating layer 50 Etching device 51 Chamber 52 Cathode-side planar electrode 53 Anode-side planar electrode 54 High-frequency power supply 55 Heating element 56 Supply pipe 57 Exhaust pipe 60 Etched body 61 Metal film 62 Oxide layer

Claims (4)

In the method of etching a metal film for etching a metal film formed on a high dielectric constant material,
By adsorbing ions or radicals containing chlorine atoms to the metal film without applying an electrical bias, a secondary product (M-Cl) is formed by the metal (M) and the chlorine atoms of the metal film. A first step of forming;
An electrical bias is applied to ions or radicals of oxygen atoms to form tertiary products (M-Cl-O) by the oxygen atoms, and etching is performed with secondary products (M-Cl) that are released by impact. And a step of etching the metal film. In the etching method of the metal film of Claim 1,
The metal film is formed of ruthenium or ruthenium oxide. A method for etching a metal film, wherein: In the etching method of the metal film of Claim 1 or 2,
The method for etching a metal film, wherein the high dielectric constant material includes an oxide of at least one metal selected from Hf, La, and Zr. In a method for manufacturing a semiconductor device, a gate electrode having a metal film laminated on a surface of a gate oxide film of a high dielectric constant material is formed on a semiconductor substrate.
Forming the gate electrode comprises:
The metal film stacked on the surface of the gate oxide film is adsorbed to ions or radicals containing chlorine atoms without applying an electrical bias, and is secondary by the metal (M) of the metal film and the chlorine atoms. A first step of forming a product (M-Cl);
An electrical bias is applied to ions or radicals of oxygen atoms to form tertiary products (M-Cl-O) by the oxygen atoms, and etching is performed with secondary products (M-Cl) that are released by impact. A method of manufacturing a semiconductor device.

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