JPH11251292A - Method and apparatus for treating with halogen-containing gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the corrosion of a material to be etched and etcher in a dry etching process using a halogen-contg. etching gas, to efficiently conduct the etching treating process. SOLUTION: In an etching chamber 3, a material 6 to be etched is dry etched using a halogen-containing an etching gas, and a high frequency discharge energy is applied only to the material 6 to be etched in the presence of O gas, etc., in the same etching chamber 3 so as to have halides existing on the material 6 to be etched removed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a material to be treated in the presence of a gas containing a halogen (for example, an etching treatment on a semiconductor substrate) by using a halogen-containing gas and an apparatus therefor.

[0002]

2. Description of the Related Art In recent years, a large scale integrat
As seen in ion) devices and the like, as the degree of integration and performance of semiconductor devices has increased, the demand for memory cell reduction technology has been increasing.

[0003] Above all, in the dry etching process of a silicon (Si) -based material or an aluminum (Al) -based material, any of requirements such as high anisotropy, high selectivity, and low damage is sacrificed. There is a strong demand for the development of technologies that can be achieved without any problems.

As an etching gas used in the dry etching process, a fluorocarbon gas or the like was used at one time. In recent years, however, gases containing various halogens such as SF ₆ , Cl ₂ , BCl ₃ , and HBr (halogen gas or halogen gas) have been used. Is referred to as "containing gas".
These are not new gases, but include any etchants such as Si, W (tungsten), and Al that are present in the material to be etched.
In the case of i, SiF ₄ , SiCl by F, Cl, Br
₄ SiBr ₄ , WF ₆ by F in the case of W, A
In the case of 1, Cl forms a product having a high vapor pressure, such as AlCl ₃ , so that the etching itself can basically be easily performed.

[0005] In order to form a sidewall protective film, which tends to be insufficient with a single gas system, for example, a gas-based material such as a decomposition product from a photoresist or a reaction product at the time of etching is used as a sidewall protective film. High anisotropy, high selectivity, low damage, and the like are ensured by controlling process parameters.

[0006]

However, several problems have been pointed out regarding the dry etching process using a halogen-based gas as described above. Of these, the problems that are particularly problematic are the corrosion of the material to be processed (particularly, the semiconductor substrate) and the corrosion of the dry etching apparatus.

Regarding the corrosion of a semiconductor substrate (wafer),
In particular, the corrosion of Al-based materials is well known. As is well known, Al atoms and Cl atoms are very reactive, and after a compound such as AlCl _X is formed and released into the atmosphere, corrosion proceeds immediately. For this reason, at present, many dry etching apparatuses used for dry etching of a laminated structure containing aluminum perform a process of removing residual Cl atoms and their compounds using an inline ashing chamber.

However, the removal of halogen-based products using an in-line ashing chamber requires transferring the material to be processed to a chamber different from the etching chamber and performing the processing in that chamber, which results in lower equipment costs. This is in line with the demand for reduction and footprint reduction.

On the other hand, corrosion of the apparatus has been pointed out in an etching process of a Si-based material. This is Si
Unlike the Al-based material etching process described above, many types of equipment do not have an in-line ashing chamber because they are not immediately corroded by halogen-based residues. doing. Therefore, Cl adsorbed on the semiconductor substrate
Atoms and Br atoms are released and have already adhered to the inner wall of the etching chamber. When released to the atmosphere, these adherents hydrate and corrode SUS-based components, and in the worst case, shorten the life of the device, It may be a source of particle generation.

Of course, it is also possible to provide an in-line ashing chamber for an etching apparatus for Si-based materials, but it is difficult to say that this is a permanent solution because it is opposed to recent demands for reduction in equipment cost and footprint. .

Therefore, in a process of etching a Si-based material, a chamber (a processing chamber: an etching chamber) for etching is mainly used for removing residual halogens (particularly halogen-based products) by a dry etching process existing on a semiconductor substrate.
In the same chamber as above), after etching,
Discharge treatment is performed to remove residual halogen. This is because a halogen atom such as Cl atom or Br atom or a halogen-based compound such as SiCl _x or SiBr _x remaining on the semiconductor substrate is converted into an excited species (reactive plasma or gas atom of a dehalogenation gas) generated by discharge energy. Molecule) or is vaporized by the heat of the discharge.

However, in this case, a problem as shown in FIG. 21 occurs. This is particularly remarkable when oxygen gas is used as a dehalogenating gas during discharge.

In general, as shown in FIG. 21A, a high-density plasma generated by a microwave generated by a magnetron discharge by a magnetron 1 and an electromagnetic field generated by a solenoid coil 4 arranges the wafer on a wafer stage 5. When the silicon wafer 6 is dry-etched, a halogen-based reaction product 100 such as SiCl _x or SiBr _x is decomposed by etching of the halogen-based etching gas or the etching of the wafer, etc., and the inner wall of the etching chamber (quartz bell jar) 3, It adheres to the wafer 6 (halogen-based reaction products attached to the wafer are not shown).

Then, as shown in FIG. 21B, the wafer stage (support electrode) 5 is placed under an oxygen gas atmosphere introduced from a gas inlet 8 for the purpose of removing halogen-based reaction products on the wafer. When a discharge process is performed by applying a high-frequency voltage from the high-frequency power supply 12 to the reaction chamber, the reactive plasma generated by the discharge also acts on the inner wall of the chamber 3. Is S
inorganic products 101 next to the iO _X like, this may drenched on the wafer 6 (however, the thickness of each product in the figure, the size is exaggerated).

The inorganic products of the SiO _X or the like attached on the wafer is secured to the wafer as particles, for example, a contact hole is blocked, or, as in such deposited between the wirings, the next stage processing This greatly affects the workability at the time, and the reliability of the device to be manufactured.

That is, in this method, although the discharge treatment is performed in the same chamber to suppress the corrosion of the material to be treated such as a semiconductor substrate, the halogen-based reaction product adhering to the inside of the treatment apparatus is not treated as an inorganic substance. However, a phenomenon has occurred in which the inorganic product falls onto the material to be processed, and a highly reliable device has not been obtained.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to prevent corrosion of a material to be processed and corrosion of an apparatus, obtain a highly reliable product, and reduce halogen-containing gas. An object of the present invention is to provide a processing method using a halogen-containing gas and an apparatus therefor, which easily realize, for example, etching processing in the presence.

[0018]

The present inventor has made intensive studies in view of the above-mentioned problems, and as a result, in particular, in a process using a halogen-containing gas, the corrosion of the material to be treated and the corrosion of the processing apparatus are reduced. At the same time, in order to obtain a highly reliable device, it is necessary to remove the halogen (particularly the halide) present in the material to be processed by a discharge that hardly acts on the site where the halogen-based product adheres in the processing apparatus. Was found to be suitable.

That is, according to the present invention, in a predetermined processing chamber,
Using a gas containing halogen, after performing a predetermined treatment on the material to be processed, in the processing chamber, in the presence of a gas for dehalogenation, substantially apply the discharge energy only to the material to be processed, The present invention relates to a processing method using a halogen-containing gas for removing halogen present in the material to be processed (hereinafter, referred to as a processing method of the present invention).

According to the processing method of the present invention, a predetermined process (for example, an etching process or a film forming process by a CVD method) is performed on a material to be processed such as a semiconductor substrate using a gas containing halogen. After that, in the processing chamber where the predetermined processing is performed, in the presence of a dehalogenating gas such as an oxygen gas or a nitrogen gas, discharge energy is applied substantially only to the material to be processed, and at the same time, the predetermined energy is applied. Since the discharge energy does not substantially act on the inner wall of the processing chamber to which the halogen-based products generated by the processing adhere,
Only the halogen (especially halide) present in the material to be treated can be efficiently removed.

As described above, in particular, corrosion of a dry etching apparatus has been pointed out in an etching process of a Si-based material.
This is because many devices do not have an inline ashing chamber, because they are not immediately corroded when the semiconductor substrate is taken out of the chamber after etching with a halogen-based gas.

However, even if an Si-based material is not provided with an in-line ashing chamber, when the semiconductor substrate after the etching process is taken out of the etching chamber, Cl atoms or the like adhering to the inner surface of the device by scattering from the semiconductor substrate are removed. Br atoms are hydrated in the atmosphere and corrode SUS-based components and the like constituting the etching apparatus. In the worst case, the life of the apparatus is shortened and particles become large.

Therefore, according to the present invention, the discharge processing is performed in the same processing chamber as the processing chamber in which the predetermined processing is performed, so that the material to be processed is not continuously exposed to the atmosphere (in particular, an oxygen atmosphere), but the halogen is continuously discharged. When the material to be processed is taken out of the processing chamber after processing, the corrosion of the material to be processed due to oxidation of the halide is prevented, and the processing of the processing chamber by the halogen atom is performed. Corrosion can be prevented. Moreover, since the discharge treatment is performed substantially only on the material to be processed (not on the inner wall of the processing chamber), the halide adhering to the inner wall of the processing chamber during the predetermined processing. Does not peel off.

Accordingly, a highly reliable product can be obtained by preventing (suppressing) the corrosion of the material to be processed and the corrosion of the processing apparatus, and at the same time, the predetermined processing and the removal of halogen present in the material to be processed. The treatment (discharge treatment) can be performed in the same treatment chamber, and the halogen can be easily removed.

In the processing method of the present invention, the “predetermined processing” means, for example, a dry etching processing or a CVD film forming processing using a halogen-containing gas as an etching gas or a source gas thereof (hereinafter, referred to as a CVD film forming processing). Similar). Further, the term “discharge treatment” means a treatment in which, in the presence of a halogen-eliminating gas, discharge energy is applied substantially only to the material to be treated to remove halogen present in the material to be treated.

According to the present invention, as a device for carrying out the processing method of the present invention with good reproducibility, a predetermined processing chamber and a gas containing halogen for performing predetermined processing on a material to be processed are supplied to the processing chamber. A discharge gas is applied to substantially only the material to be treated in the presence of a dehalogenating gas in the first gas introduction chamber to be introduced into the processing chamber, and halogen present in the material to be treated is removed. And a second gas introducing means for introducing the dehalogenating gas into the processing chamber. The processing apparatus uses a halogen-containing gas (hereinafter, referred to as a processing apparatus of the present invention). is there.

According to the processing apparatus of the present invention, the processing chamber and the gas containing halogen for performing a predetermined process (for example, an etching process or a film forming process by a CVD method) on a material to be processed such as a semiconductor substrate. A first gas introduction chamber for introducing the gas into the processing chamber, and in this processing chamber, in the presence of a dehalogenation gas such as an oxygen gas or a nitrogen gas, discharge energy is applied substantially only to the material to be processed. Discharge means for removing halogen present in the material to be processed, and second gas introducing means for introducing the gas for dehalogenation into the processing chamber, wherein discharge energy is applied only to the material to be processed. The discharge energy does not substantially act on the inner wall of the processing chamber to which the halogen-based products and the like generated by the predetermined processing adhere. (Especially halides) can be efficiently removed, so that the corrosion of the material to be treated and the corrosion of the processing equipment can be suppressed, and a highly reliable product can be obtained. The discharge treatment can be performed in the same processing chamber, and the halogen can be removed by an apparatus having a simple configuration.

In the processing apparatus of the present invention, the first gas inlet and the second gas inlet may be arranged at different positions even if they are arranged at the same position. There may be.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The processing method and the processing apparatus of the present invention (hereinafter, may be referred to as "the present invention").
A preferred embodiment will be described.

In the present invention, after the material to be processed is dry-etched into a predetermined fine pattern using the gas containing halogen in the processing chamber, the presence of the gas for dehalogenation in the processing chamber is performed. It is desirable that high frequency discharge energy be applied substantially only to the material to be processed to remove the halogen adhering to the material to be processed.

That is, the present invention is particularly preferably applied to a dry etching process (and its apparatus). For example, in the processing chamber, C is used as an etching gas.
Using a halogen-containing gas such as l ₂ gas, HBr gas, or BCl ₃ gas, dry-etch a material to be processed such as a Si-based material or an Al-based material provided on a semiconductor substrate into a predetermined fine pattern in the presence thereof. After processing, the high-frequency discharge energy is applied substantially only to the material to be processed in the same chamber as the processing chamber in the presence of a dehalogenating gas such as oxygen gas, nitrogen gas, hydrogen gas, etc. Halogen (for example, halogen atoms such as Cl and Br, and halides such as AlCl _x , CCl _x , SiCl _x and SiBr _x ) attached to the processing material can be removed. The high frequency energy is, for example, RF bias 1
At 3.56 MHz, it is desirable to apply a power of 100 W or more and a time of 5 seconds or more.

In particular, an electrode is provided on the material to be processed, and this electrode (hereinafter sometimes referred to as a first electrode) and
It is desirable that a high-frequency voltage is applied between an electrode disposed in the vicinity of the material to be processed (hereinafter, sometimes referred to as a second electrode) to generate the high-frequency discharge. In particular, it is more preferable that the second electrode is provided at a portion where the halogen-based product generated on the inner wall of the processing chamber during the predetermined processing does not exist. Further, when a high-frequency voltage applied between the first electrode and the second electrode is applied only to the first electrode, the high-frequency discharge energy substantially acts only on the first electrode. (Ie, without applying the discharge energy to the portion of the processing chamber to which the halogen adheres), so that the high-frequency discharge energy is applied only to the material to be processed disposed on the first electrode. Is possible.

More specifically, as in a plasma separation type etching method in which a plasma generation region and an etching region are different, a reactive plasma of the halogen-containing gas is generated, and the reactive plasma is applied to the support electrode. After the dry etching process is performed by acting on the material to be processed, the support electrode (first electrode) and a counter electrode (second electrode) arranged near the support electrode
The high-frequency voltage can be applied between the two to generate the high-frequency discharge in a region different from the reactive plasma generation region. At this time, it is desirable that the counter electrode be grounded.

Alternatively, as in an etching method using a parallel plate, a reactive plasma of the halogen-containing gas is applied between a supporting electrode of the material to be processed and a counter electrode disposed opposite to the supporting electrode. After the dry etching is performed by causing the reactive plasma to act on the material to be processed, the high-frequency voltage is applied only to the support electrode, and between the counter electrode and the support electrode. Thus, the high-frequency discharge can be generated substantially only in the vicinity of the support electrode.

In the present invention, the dehalogenating gas is selected from the group consisting of oxygen gas (O ₂ ), nitrogen gas (N ₂ ), hydrogen gas (H ₂ ) and inert gas (Ar, He, etc.). It may be at least one gas selected. At the time of the discharge treatment, the plasma (or excited species, ions, etc.) of these gases is applied to the material to be treated, whereby the halogen (particularly the halide) present in the material to be treated is converted to the reactive material. It can be replaced by atoms (or molecules) in the plasma, or it can be vaporized by its discharge heat.

As an etching apparatus used for the above-mentioned dry etching processing, an apparatus for generating reactive plasma for the above-mentioned predetermined processing by a microwave by a magnetron [for example, a magnetic field microwave plasma etching apparatus, an ECR (electron cyclotron resonance: Electron cyclotron) plasma etching apparatus]. Further, an apparatus (for example, an inductively coupled plasma etching apparatus or the like) that generates reactive plasma for the predetermined processing by using a high-frequency voltage applied to the inductively coupled coil may be used. An apparatus (such as a helicon wave plasma etching apparatus) that generates reactive plasma for the predetermined processing by an action may be used.

As described above, in the present invention, it is particularly preferable to apply the present invention to a plasma separation type etching apparatus in which the reactive plasma generation region and the work material installation region are separated.

Further, an apparatus for generating a reactive plasma for the predetermined processing by means of a high-frequency voltage applied between the material to be processed and the counter electrode [for example, a parallel plate type RIE (reactive ion etching: reaction). Ion etching) apparatus or the like].

Further, in the present invention, when the processing is performed while the material to be processed is supported by an electrostatic chuck, the residual energy at the time of the electrostatic chuck can also be removed by the discharge energy. Therefore, in the processing apparatus of the present invention, it is desirable to provide a clamp for mechanically fixing the material to be processed. Generally, for the purpose of cooling a material to be processed (eg, a wafer) or the like, the material to be processed and its support (eg, a wafer stage) are closely adhered to each other by an electrostatic chuck in order to improve thermal conductivity.
It is fixed. For the purpose of further improving the thermal conductivity, a gas (He, N _2, or the like) having a high thermal conductivity may be introduced between the material to be processed and the support thereof (in some cases). That is, the gas fills a slight gap between the material to be processed and its support). Therefore, when such a method is employed, if the introduction of the gas having a high thermal conductivity (backside gas) is stopped immediately before the residual charge is eliminated, the material to be processed does not have to float, so that the clamp is necessarily required. Not necessarily.

Further, in the present invention, the dry etching process can be performed on a predetermined film (film to be processed) formed on the semiconductor substrate.

The film to be processed on the semiconductor substrate is, for example,
As described later, the gate electrode may be a polysilicon wiring (polycide wiring) or an aluminum wiring. However, the present invention is not limited to the etching step for forming these wirings, but may be applied to various semiconductor manufacturing processes using a halogen-containing gas, for example, a p-well type CMO.
In the case of an S semiconductor device manufacturing process, etching of an oxide film for forming a p-well, etching of a nitride film for forming an element isolation region, etching for forming a gate oxide film, etching for forming a gate electrode, It can be applied to various etching processes such as etching for forming source / drain regions. Further, the present invention can be applied to various processes of a CVD method (for example, formation of a barrier metal, formation of an oxide film, formation of a silicon nitride film, and the like) using a halogen-containing gas as a source gas. Further, as a material to be processed, the present invention can be applied to, for example, an etching process of a glass material or the like in addition to the semiconductor substrate.

In the present invention, the halogen (residual halogen) present in the material to be treated is removed, and after the material to be treated is taken out of the processing chamber, the material is treated under the same degassing atmosphere as described above. , It is possible to remove the halogen-based product attached to the inner wall of the processing chamber.

Next, various plasma etching apparatuses according to the present invention will be described with reference to FIGS.

First, an RF (radio frequency) bias applying type ECR plasma etching apparatus shown in FIG. 1 will be described.

In this device, the microwave generated by the magnetron 1 is applied to the waveguide 2 as shown by the arrow A in the figure.
It is configured to reach the wafer 6 on the wafer stage 5 via the quartz bell jar 3 as the processing chamber. A solenoid coil (electromagnetic coil) 4 is arranged around the quartz bell jar 3 so that an electromagnetic field is generated inside the quartz bell jar. , A high-density reactive plasma for etching is generated.

The quartz bell jar (predetermined chamber) 3 includes:
In the vicinity of a wafer 6 as a material to be processed, a gas inlet 8 as the first gas inlet and a gas inlet 8 as the second gas inlet
Is provided, and a predetermined gas 9 is introduced at a predetermined flow rate and a predetermined pressure. Therefore, a halogen-containing gas as an etching gas is introduced during the etching process of the wafer 6, and a dehalogenating gas such as an oxygen gas is introduced during the discharge process. Further, the wafer stage 5 is connected to a high-frequency power supply 12 and is configured as a support electrode that also serves as a support member for the wafer 6 during the etching process and the discharge process.

In the quartz bell jar 3, high-frequency discharge energy is applied substantially only to the wafer 6 to remove halogens (particularly halides) existing on the wafer 6 by the above-mentioned predetermined processing. An earth ring 13 forming a discharging means is provided. This earth ring is arranged in a region other than the region where the reactive plasma is generated by the etching process so as to generate a high-frequency discharge at the time of the discharge process. 6 and a ring around the wafer stage 5. Therefore, at the time of the discharge processing, a high-frequency power is supplied between the wafer stage 5 and the earth ring 13 by the high-frequency power supplied from the high-frequency power supply 12, and the high-frequency discharge further causes a dehalogenation introduced from the gas inlet. A reactive plasma of the working gas is generated and acts on the wafer 6 to achieve the removal of the halogen present on the wafer 6.

The wafer 6 is fixed on the wafer stage 5 by a clamp 7, and is also fixed by an electrostatic chuck during the etching process. Further, the quartz bell jar 3 is provided with a gas exhaust port 10 and is provided with a quartz bell jar 3 by a turbo molecular pump or the like.
Degassing (exhausting) is performed so that the inside becomes a predetermined pressure. Further, the earth ring 13 may be grounded as shown, or may be connected to the high-frequency power supply 12.

Next, the inductively coupled plasma (ICP:
An etching apparatus of the inductively coupled plasma type will be described.

In this apparatus, at the time of the etching process, for example, 13.56 MHz is applied to the inductive coupling coil 22 wound on the quartz plate 21 from the high frequency power source 23 in a mosquito coil.
Is applied, a high-density reactive plasma of a halogen-containing gas for etching processing is formed between the quartz plate 21 and the wafer stage 25.

The processing chamber 20 is provided with the first gas inlet 24 and the gas inlet 24 as the second gas inlet in the vicinity of a wafer 26 as a material to be processed. Is introduced at a predetermined flow rate and pressure. Therefore, similarly to the above-mentioned RF bias application type ECR plasma etching apparatus (FIG. 1), a halogen-containing gas is introduced as an etching gas during the etching process, and a halogen-containing gas such as oxygen gas is discharged during the discharging process. Gas is introduced. Further, the wafer stage 25 is connected to a high-frequency power supply 28 and is configured as a support electrode that also serves as a support member for the wafer 26 during the etching process and the discharge process.

In the processing chamber 20, high-frequency discharge energy is applied to substantially only the wafer 26,
An earth ring 29 forming a discharge means for removing halogen (particularly halide) present on the wafer 26 by the etching process is provided. This earth ring is arranged in a ring shape at a position that generates a high-frequency discharge during the discharge process in a region different from a region where reactive plasma is generated by the etching process,
The inner wall of the quartz plate 21 is arranged around the wafer 26 and the wafer stage 25. Therefore, at the time of the discharge process, a high-frequency power is supplied between the wafer stage 25 and the earth ring 29 by the high-frequency power supplied from the high-frequency power supply 28, and the high-frequency discharge is introduced from the gas inlet 24 by the high-frequency discharge. A reactive plasma of the dehalogenating gas is generated, which acts on the wafer 26 to achieve the removal of the halogen present on the wafer 26.

The wafer 26 is placed on the wafer stage 25
It is fixed on the upper side by a clamp 27, and is also fixed by an electrostatic chuck during the etching process. Further, a gas exhaust port 30 is provided in the processing chamber 20, and degassing is performed by a turbo molecular pump or the like so that the inside of the processing chamber 20 has a predetermined pressure. Further, the earth ring 29 may be grounded as shown,
It may be connected to the high frequency power supply 28.

Next, the helicon wave plasma type etching apparatus shown in FIG. 3 will be described.

In this apparatus, when RF (for example, 13.56 MHz) is applied to the antenna 31 by the source power supply 34, the interaction with electrons in the magnetic field formed by the solenoid coil 33 causes the whistler wave (helicon wave) in the source chamber 32. ) Is generated, and the resulting high-density plasma reaches the wafer 37 disposed in the processing chamber 43 in which the multipole magnet 35 is disposed.

In the processing chamber 43, the first gas inlet 41 and the gas inlet 41 as the second gas inlet are provided in the vicinity of the wafer 37 as a material to be processed. Is introduced at a predetermined flow rate and pressure. Therefore, similarly to the above-described RF bias application type ECR plasma etching apparatus (FIG. 1) and the inductively coupled plasma type etching apparatus (FIG. 2),
At the time of the etching treatment, a halogen-containing gas is introduced as an etching gas, and at the time of the discharge treatment, a gas for removing halogen such as an oxygen gas or a nitrogen gas is introduced. Further, the wafer stage 36 is connected to a high-frequency power supply 38 and is configured as a support electrode that also serves as a support member for the wafer 37 during the etching process and the discharge process.

Then, in the processing chamber 43, high-frequency discharge energy is applied substantially only to the wafer 37,
An earth ring 40 forming a discharge means for removing halogen (particularly halide) present on the wafer 37 by the etching process is provided. The earth ring is disposed in a region different from a region where reactive plasma is generated by the predetermined process, so as to generate a high-frequency discharge during the discharge process, and is an inner wall of the processing chamber 43, It is arranged in a ring shape around the wafer 37 and the wafer stage 36. Therefore, at the time of the discharge processing, a high-frequency power is supplied between the wafer stage 36 and the earth ring 40 by the high-frequency power supplied from the high-frequency power supply 38, and the high-frequency power is discharged from the gas inlet 41 by the high-frequency discharge. Reactive plasma of a halogen gas is generated, and acts on the wafer 37 to remove the halogen present on the wafer 37.

The wafer 37 is mounted on the wafer stage 36.
It is fixed above by a clamp 39, and is also fixed by an electrostatic chuck at the time of etching processing. The processing chamber 43 is provided with a gas exhaust port 42, and the processing chamber 4 is provided by a turbo molecular pump or the like.
Degassing is performed so that the inside of the chamber 3 has a predetermined pressure. further,
The earth ring 40 may be grounded as shown, or may be connected to the high frequency power supply 38.

Next, the parallel plate type etching shown in FIG. 4 will be described.

In this apparatus, in particular, the high frequency from the high frequency power supply 56 is divided and applied to the wafer stage 51 serving as the lower electrode and the upper electrode 50 arranged opposite to the lower stage, so that a relatively high frequency for the etching process is obtained. This is a mechanism that can irradiate the plasma of the density to the wafer 52.

The first gas inlet and the gas inlet 54 as the second gas inlet are provided in the vicinity of the wafer 52 as a material to be processed. It is configured to be introduced at a flow rate and pressure. Therefore, like the RF bias application type ECR plasma etching apparatus (FIG. 1), the inductively coupled plasma type etching apparatus (FIG. 2), and the helicon wave plasma type etching apparatus (FIG. 3), the etching is performed during the etching process. A halogen-containing gas is introduced as a gas, and a gas for dehalogenation such as oxygen gas is introduced during the discharge treatment. Further, the wafer stage 52 is connected to a high-frequency power supply 56 and is configured as a support electrode that also serves as a support member for the wafer 52 during the etching process and the discharge process.

During the etching process, a high-frequency voltage is applied to the upper electrode 50 and the lower electrode 51 substantially uniformly, so that the reactive plasma of the etching gas is uniformly applied between the upper electrode 50 and the lower electrode 51. The wafer 52 is etched and the wafer stage (lower electrode) 51 and the upper electrode 50 are subjected to the high frequency power supplied from the high frequency power supply 56 during the discharge processing.
And a reactive plasma of the dehalogenating gas introduced from the gas inlet 41 is generated by the high-frequency discharge.
If 0 is grounded, the energy of the reactive plasma is low near the upper electrode 50, and the action of the reactive plasma on the halogen-based product deposited on the upper electrode 50 (this corresponds to so-called sputtering) is suppressed. Only the halogen-based products on the wafer 52 can be removed.

The wafer 52 is fixed on a wafer stage (lower electrode) 51 by a clamp 53, and is also fixed by an electrostatic chuck during the etching process. Further, the processing chamber 57 is provided with a gas exhaust port 42, and is provided with a turbo molecular pump or the like.
Degassing is performed so as to be a predetermined pressure.

In the above-described various etching apparatuses, although not shown, the wafer stage (or lower electrode) has a structure in which a coolant for controlling temperature (for example, Fluorinert: trade name) is circulated. It is assumed that an electric chuck is installed.

[0065]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples.

Embodiment 1 In this embodiment, the discharge treatment is performed in an etching step of forming a tungsten-polycide (W-polycide) wiring on a silicon substrate using the RF bias type ECR plasma etching apparatus shown in FIG. This is an example in which is applied.

First, the sample used in this embodiment has a laminated structure shown in FIG.
After forming the gate oxide film (SiO ₂ ) 62 by thermal oxidation,
The polysilicon film 63 is formed on the 100nm thickness by the low pressure CVD method, then, a WSi _X film 64 by plasma CVD 1
The photoresist 65 is formed in a predetermined fine pattern by forming a layer having a thickness of 00 nm and further applying a photoresist by spin coating, and then performing gate patterning with a width of 0.25 μm using an excimer stepper.

[0068] After this, in the etching apparatus shown in FIG. 1, under the following conditions, WSi _X film 64 and the polysilicon film 63 - where the etching of (tungsten polycide) was carried out stepwise, as shown in FIG. 6 It became a shape.

<Main etching step> Gas type and flow rate: Cl ₂ / O ₂ = 75/6 sccm Pressure: 0.4 Pa Microwave output (2.45 GHz): 1200 W RF bias (800 kHz): 70 W Wafer temperature: 20 ° C.

<Overetching Step> Gas type and flow rate: Cl ₂ / O ₂ = 75/6 sccm Pressure: 0.4 Pa Microwave output (2.45 GHz): 1200 W RF bias (800 kHz): 30 W Wafer temperature: Over 20 ° C. Etch: 40%

At this time, as shown in FIG. 6, a halogen-based side wall protective film 6 containing SiCl _X as a main component is formed on the pattern side walls.
6 was deposited (however, the film thickness in the figure is exaggerated and shown thickly). Although not shown, a halogen-based product having the same component as that of the halogen-based side wall protective film 66 adhered to the vicinity of the upper inner wall of the quartz bell jar 3.

Thereafter, in the same chamber, the following residual halide (here, SiC in the side wall protective film)
l _x ) When discharge treatment was performed for removal, the shape was as shown in FIG. 7. <Discharge treatment conditions> Gas type and flow rate: O ₂ = 20 sccm Pressure: 2.0 Pa Microwave output (2.45 GHz): 0 W RF bias (800 kHz): 100 W Wafer temperature: 20 ° C. Time: 10 seconds

Under such discharge processing conditions, a high-frequency discharge occurs between the wafer stage 5 and the earth ring 13 in FIG. 1 to remove the residual halide on the wafer 6 and, at the same time, to remove the inner wall of the quartz bell jar 3. Until the plasma hardly reached, no particle generation was observed. Further, as shown in FIG. 7, the deposited film on the pattern side wall after the discharge treatment changed to an inorganic side wall protective film 67 containing SiO _X as a main component. Furthermore, under the above conditions,
The residual charge can be removed at the time of the electrostatic chuck.

Thereafter, by combining the cleaning step and the ashing step using an HF-based gas, a tungsten-polycide wiring 68 was formed in a good processed shape as shown in FIG.

As described above, according to the present embodiment, good etching of the Si-based material provided on the semiconductor substrate can be realized, and both device characteristics and device reliability can be achieved.

Example 2 In this example, tungsten was deposited on a silicon substrate using the inductively coupled plasma type etching apparatus shown in FIG.
This is an example in which the discharge treatment is applied to an etching step for producing a polycide (W-polycide) wiring.

First, the sample used in this embodiment has a laminated structure shown in FIG.
After forming the gate oxide film (SiO ₂ ) 62 by thermal oxidation,
The polysilicon 63 is formed to 100nm thickness by the low pressure CVD method, then, a WSi _X film 64 by plasma CVD 10
The photoresist 65 is formed in a predetermined fine pattern by performing a gate patterning with a width of 0.25 μm using an excimer stepper after applying a photoresist by spin coating to form a photoresist 65 with a thickness of 0 nm.

[0078] After this, in the etching apparatus shown in FIG. 2, under the following conditions, WSi _X film 64 and the polysilicon film 63 - was carried out etching (tungsten polycide) stepwise, as shown in FIG. 10 It became a shape.

<Main etching step> Gas type and flow rate: Cl ₂ / O ₂ = 100/5 sccm Pressure: 0.4 Pa Source output (13.56 MHz): 300 W RF bias (13.56 MHz): 150 W Wafer temperature: 60 ° C.

<Overetching Step> Gas type and flow rate: Cl ₂ / HBr / O ₂ = 50/50/5 sccm Pressure: 0.4 Pa Source output (13.56 MHz): 300 W RF bias (13.56 MHz): 50 W Wafer Temperature: 60 ° C Overetch: 40%

[0081] At this time, as shown in FIG. 10, the pattern sidewall SiCl _X, is halogen-based sidewall protective film 70 composed mainly of SiBr _X was deposited (however, the thickness in the figure indicate thicker exaggerated ing). Although not shown, the halogen-based side wall protective film 7 is provided near the upper inner wall of the processing chamber 20.
A halogen-based product having the same component as that of 0 was attached.

Then, in the same chamber, the following residual halide (here, SiC in the side wall protective film)
1 _x , SiBr _x ) was subjected to a discharge treatment to remove it, resulting in a shape as shown in FIG. <Discharge treatment conditions> Gas type and flow rate: N ₂ = 20 sccm Pressure: 1.0 Pa Source output (13.56 MHz): 0 W RF bias (13.56 MHz): 200 W Wafer temperature: 60 ° C. Time: 5 seconds

Under such discharge processing conditions, a high-frequency discharge is generated between the wafer stage 25 and the earth ring 29 in FIG. 2 to remove the residual halide on the wafer 26 and, at the same time, to reach the inner wall of the processing chamber 20. Since the reactive plasma at the time of discharge hardly reached, no particles were generated. Further, as shown in FIG. 11, the deposited film on the pattern side wall after the discharge treatment changed to an inorganic side wall protective film 71 containing SiN _X as a main component. Further, under the above conditions, the residual charge can be removed at the time of the electrostatic chuck.

Thereafter, a tungsten-polycide wiring 72 was formed in a good processed shape as shown in FIG. 12 by a combination of a cleaning step and an ashing step using an HF-based gas.

As described above, according to the present embodiment, a favorable etching treatment of the Si-based material provided on the semiconductor substrate can be realized, and both device characteristics and device reliability can be achieved.

Embodiment 3 This embodiment is an example in which the above-described discharge treatment is applied to an etching step of forming an aluminum wiring on a silicon substrate using the helicon wave plasma etching apparatus shown in FIG.

First, the sample used in this embodiment is shown in FIG.
After a SiO ₂ film 82 is formed on a silicon substrate 81 by plasma CVD, TiN
Metal 83 made of Al, an Al-Cu layer 84 made of aluminum and copper, and an antireflection film 85 made of TiN
By a sputtering method.
The photoresist 86 is sequentially formed so as to have a thickness of 100 nm, and further, a photoresist is applied by a spin coating method, and then a 0.3 μm-width wiring pattern is performed by using an excimer stepper to form a photoresist 86 into a predetermined fine pattern. is there.

Thereafter, the Al wiring (that is, the barrier metal 8
3 / Al-Cu layer 84 / anti-reflection film 85) was etched to obtain the shape shown in FIG.

<Main etching step> Gas type and flow rate: Cl ₂ / BCl ₃ = 100/100 sccm Pressure: 0.5 Pa Source output (13.56 MHz): 1500 W RF bias (400 kHz): 150 W Wafer temperature: 20 ° C.

<Overetching Step> Gas type and flow rate: Cl ₂ / BCl ₃ = 150/50 sccm Pressure: 0.5 Pa Source output (13.56 MHz): 1500 W RF bias (13.56 MHz): 50 W Wafer temperature: 20 ° C. Overetch: 30%

[0091] At this time, as shown in FIG. 14, the pattern side wall and deposited halogenated sidewall protective film 87 to AlCl _X, a CCl _X as a main component (however, the thickness in the figure indicate thicker exaggerated ing). Although not shown, the processing chamber 4
3, the halogen-based side wall protective film 87
And a halogen-based product having the same components as

Thereafter, in the same chamber, the following residual halide (here, AlCl of the side wall protective film)
_X , CCl _x ).
The shape was as shown in FIG. <Discharge treatment conditions> Gas type and flow rate: O ₂ = 50 sccm Pressure: 1.0 Pa Source output (13.56 MHz): 0 W RF bias (400 kHz): 150 W Wafer temperature: 20 ° C. Time: 10 seconds

Under such discharge processing conditions, a high-frequency discharge is generated between the wafer stage 36 and the earth ring 40 in FIG. 3 to remove the residual halide on the wafer 37 and at the same time reach the inner wall of the processing chamber 43. No particles were generated because the reactive plasma generated hardly reached. Further, as shown in FIG. 15, the deposited film on the pattern side wall after the discharge treatment changed to an inorganic side wall protective film 88 containing AlO _X as a main component. Further, under the above conditions, the residual charge can be removed at the time of the electrostatic chuck.

Thereafter, by a combination of the washing step and the ashing step with the organic solvent, the aluminum wiring 90 was formed in a good processed shape as shown in FIG.

As described above, according to the present embodiment, an excellent etching treatment of the Al-based material provided on the semiconductor substrate can be realized, and both device characteristics and device reliability can be achieved.

Embodiment 4 This embodiment is an example in which the above-described discharge treatment is applied to an etching step of forming an aluminum wiring on a silicon substrate by using the parallel plate type etching apparatus shown in FIG.

First, the sample used in this embodiment is shown in FIG.
After a SiO ₂ film 82 is formed on a silicon substrate 81 by plasma CVD, TiN
Metal 83 made of Al, an Al-Cu layer 84 made of aluminum and copper, and an antireflection film 85 made of TiN
By a sputtering method.
The photoresist 86 is sequentially formed so as to have a thickness of 100 nm, and further, a photoresist is applied by a spin coating method, and then a 0.3 μm-width wiring pattern is performed by using an excimer stepper to form a photoresist 86 into a predetermined fine pattern. is there.

Thereafter, in the etching apparatus shown in FIG. 4, Al wiring (that is, barrier metal 8
3 / Al-Cu layer 84 / antireflection film 85) was etched to obtain the shape shown in FIG.

<Main etching step> Gas type and flow rate: Cl ₂ / BCl ₃ = 200/300 sccm Pressure: 5 Pa RF output (400 kHz): 1500 W Upper / lower ratio: 60% / 40% Wafer temperature: 20 ° C.

<Overetching Step> Gas type and flow rate: Cl ₂ / BCl ₃ = 250/50 sccm Pressure: 5 Pa RF output (400 kHz): 800 W Top / bottom ratio: 60% / 40% Wafer temperature: 20 ° C. Overetch: 30%

[0102] At this time, as shown in FIG. 18, the pattern sidewall AlCl _X, is halogen-based sidewall protective film 92 composed mainly of CCl _X is deposited (however, the thickness in the figure indicate thicker exaggerated ing). Although not shown, the processing chamber 5
7, the halogen-based side wall protective film 92
And a halogen-based product of the same component as the above.

Thereafter, in the same chamber, the following residual halide (here, AlCl of the side wall protective film)
_X , CCl _x ).
The shape was as shown in FIG. <Discharge treatment conditions> Gas type and flow rate: Ar = 200 sccm Pressure: 3 Pa RF output (400 kHz): 300 W Upper / lower ratio: 0% / 100% Wafer temperature: 20 ° C. Time: 5 seconds

Under such discharge processing conditions, a high-frequency discharge is generated between the wafer stage (lower electrode) 51 and the upper electrode 50 in FIG. 50, the ion energy was low, and the high-frequency discharge did not substantially act. That is, the sputter rate of the deposit attached to the vicinity of the upper electrode 50 in the processing chamber 57 was suppressed, so that almost no particles were generated. . Further, as shown in FIG. 19, the deposited film on the pattern side wall after the discharge treatment changed to an inorganic side wall protective film 93 containing Al and Ti as main components. further,
Under the above conditions, it was also possible to remove the residual charges at the time of the electrostatic chuck.

As a subsequent step, as shown in FIG. 20, a good aluminum wiring 94 is obtained by a combination of a cleaning step and an ashing step using an organic solvent.
Could be formed.

As described above, also in the present embodiment, a favorable etching treatment of the Al-based material provided on the semiconductor substrate could be realized, and both device characteristics and device reliability could be achieved.

Although the present invention has been described based on the four embodiments, it is needless to say that the present invention is not limited to the above-described embodiments, but includes an etching plasma source, an apparatus configuration, a sample structure, and a process. Conditions can be appropriately selected without departing from the gist of the present invention.

Further, as described above, in the present embodiment, in the etching process using the gas containing halogen, in order to suppress the corrosion of the semiconductor substrate (wafer), it is difficult to act on the inner wall of the chamber, and the plasma generation is difficult. The point is to remove the halide on the semiconductor substrate by RF discharge on the substrate side different from the side.

Conventionally, in the etching process of an Al-based material, a discharge process in the presence of a fluorine-based gas or an oxygen-based gas has been known in order to prevent so-called corrosion. Very recently, similar discharge treatments have begun to be implemented. However, in both etching treatments, the discharge for preventing corrosion involves a reaction that oxidizes halogen-based reaction products attached to the chamber wall surface or changes them into substances having a low vapor pressure. Had occurred in large numbers.

Therefore, in the present embodiment, the generation of the particles is suppressed by performing a discharge treatment that mainly acts on the semiconductor substrate and does not act on the inner wall surface of the chamber. The discharge at that time is to apply RF to the substrate side different from the plasma generation side, which is a so-called cathode couple system. In this case, the material, surface area, and position of the earth will also be important points, but there is no problem if the chamber design is devised including the positional relationship with the wall surface to which the reaction product easily adheres. More specifically, a sufficient effect can be obtained by providing a certain distance between the substrate and the reactive plasma generation region where the reaction products are likely to adhere, and disposing the ground around the substrate electrode.

Further, as an advantage of this embodiment, as described above, since it can be combined with the single-pole type electrostatic chuck residual charge removing discharge step, the throughput can be sufficiently reduced in the range of the etching process.

In this embodiment, the so-called remote plasma method (plasma separation type etching method) in which the plasma generation side and the substrate side are separated, as well as the etching apparatus of the high density plasma type which is mainly used recently, is used. )
Can be applied to

[0112]

According to the processing method of the present invention, a predetermined process is performed on a material to be processed such as a semiconductor substrate using a gas containing halogen, and then the predetermined process is performed. In a room, in the presence of a dehalogenating gas such as an oxygen gas or a nitrogen gas, discharge energy is applied substantially only to the material to be processed, so that the halogen-based product generated by the predetermined process adheres. The discharge energy does not substantially act on the interior wall, and only the halogen present in the material to be treated can be efficiently removed,
Therefore, corrosion of the material to be processed and corrosion of the processing apparatus are suppressed, and a highly reliable product can be obtained. At the same time, the predetermined process and the process of removing halogen present in the material to be processed are performed in the same processing chamber. And the halogen can be easily removed.

According to the processing apparatus of the present invention, the processing chamber and the first gas introduction chamber for introducing a gas containing halogen into the processing chamber for performing a predetermined processing on a material to be processed such as a semiconductor substrate. In the processing chamber, in the presence of a dehalogenating gas such as an oxygen gas or a nitrogen gas, a discharge energy is applied to substantially only the material to be processed to remove halogen present in the material to be processed. Means, and the second gas introduction means for introducing the dehalogenation gas into the processing chamber, when performing the discharge treatment,
The discharge energy does not substantially act on the inner wall of the processing chamber to which the halogen-based product or the like generated by the predetermined processing adheres, and it is possible to efficiently remove only the halogen present in the material to be processed. It is possible to suppress the corrosion of the material to be processed and the corrosion of the processing apparatus, and thus a highly reliable product can be obtained.At the same time, the predetermined processing and the discharge processing can be performed in the same processing chamber. The removal of the halogen can be performed by an apparatus having a simple configuration.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a main part of an RF bias application type ECR plasma etching apparatus that can be used in the processing method of the present invention.

FIG. 2 is a schematic view of a main part of the same inductively coupled plasma (ICP) type etching apparatus.

FIG. 3 is a schematic view of a main part of the helicon wave plasma type etching apparatus.

FIG. 4 is a schematic diagram of a main part of the parallel plate type etching apparatus.

FIG. 5 is a schematic diagram showing one manufacturing step when manufacturing a tungsten-polycide wiring based on Example 1 of the present invention.

FIG. 6 is a schematic view showing another manufacturing step of manufacturing a tungsten-polycide wiring.

FIG. 7 is a schematic diagram showing another manufacturing step of manufacturing a tungsten-polycide wiring.

FIG. 8 is a schematic diagram showing another manufacturing step of manufacturing a tungsten-polycide wiring.

FIG. 9 is a schematic diagram showing one manufacturing step when manufacturing a tungsten-polycide wiring based on Example 2 of the present invention.

FIG. 10 is a schematic diagram showing another manufacturing step of manufacturing a tungsten-polycide wiring.

FIG. 11 is a schematic view showing another manufacturing step of manufacturing a tungsten-polycide wiring.

FIG. 12 is a schematic diagram showing another manufacturing step of manufacturing a tungsten-polycide wiring.

FIG. 13 is a schematic diagram showing one manufacturing step when manufacturing an aluminum wiring based on Embodiment 3 of the present invention.

FIG. 14 is a schematic view showing another manufacturing step of manufacturing an aluminum wiring.

FIG. 15 is a schematic view showing another manufacturing step of manufacturing the aluminum wiring.

FIG. 16 is a schematic diagram showing another manufacturing step of manufacturing the aluminum wiring.

FIG. 17 is a schematic diagram showing one manufacturing step when manufacturing an aluminum wiring based on Example 4 of the present invention.

FIG. 18 is a schematic view showing another manufacturing step of manufacturing an aluminum wiring.

FIG. 19 is a schematic view showing another manufacturing step of manufacturing the aluminum wiring.

FIG. 20 is a schematic view showing another manufacturing step of manufacturing the aluminum wiring.

FIG. 21 is a schematic view (A) showing the inside of a device after etching a Si-based material using a normal RF bias application type ECR plasma etching device, and generating a high-frequency discharge inside the device. FIG. 7B is a schematic diagram (B) of a main part showing a state when the display is folded.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Magnetron, 2 ... Waveguide, 3 ... Quartz bell jar (processing chamber), 4, 33 ... Solenoid coil, 5, 25,
36 wafer stage, 6, 26, 37, 52 wafer, 7, 27, 39, 53 clamp, 8, 24, 4
1, 54: gas inlet, 9: introduced gas, 10, 30, 4
2, 55 ... gas outlet, 11 ... exhaust gas, 12, 23,
28, 34, 38, 56 ... high frequency power supply, 13, 29, 4
0: earth ring, 20, 43, 57: processing chamber, 21:
Quartz plate, 22 ... inductive coupling coil, 31 ... antenna, 32
... source chamber, 34 ... source power supply, 35 ... multipole magnet, 50 ... upper electrode, 51 ... lower electrode, 61 ...
Silicon substrate, 62 ... gate oxide film, 63 ... polysilicon film, 64 ... WSi _x film, 65,86 ... photoresist, 66 ... halogenated sidewall protective film composed mainly of SiCl _x, mainly of 67 ... SiO _x , 68, 72 ... tungsten-polycide wiring, 70
... Halogen-based side wall protective film mainly composed of SiCl _x and SiBr _x , 71. Inorganic inorganic side wall protective film mainly composed of SiN _x , 81 silicon substrate, 82 SiO ₂ film 83
... Barrier metal layer, 84 ... Aluminum-copper wiring layer, 8
5 ... Anti-reflection film, 87 ... Halogen-based side wall protective film containing AlCl _x and CCl _x as main components, 88 ... Inorganic side wall protective film mainly containing AlO _x , 90, 94 ... Aluminum wiring, 92 ... AlCl _x , A halogen-based side wall protective film mainly containing CCl _x , 93 ... an inorganic side wall protective film mainly containing Al and Ti, 100 ... SiCl _x and SiBr
The reaction product mainly composed of _x, product composed mainly of 101 ... SiO _x

Claims (26)

[Claims] After subjecting a material to be treated to a predetermined treatment using a gas containing halogen in a predetermined treatment chamber, the material is substantially treated in the treatment chamber in the presence of a dehalogenation gas. Apply discharge energy only to the material to be treated,
A processing method using a halogen-containing gas for removing halogen present in the material to be processed. 2. After the material to be processed is dry-etched into a predetermined fine pattern using the halogen-containing gas in the processing chamber, the material is processed in the processing chamber in the presence of the dehalogenating gas. 2. The processing method using a halogen-containing gas according to claim 1, wherein high-frequency discharge energy is applied substantially only to the material to be processed to remove halogen adhering to the material to be processed. 3. An electrode is disposed on the material to be processed, and a high-frequency voltage is applied between the electrode and an electrode disposed near the material to be processed to generate the high-frequency discharge. The treatment method using a halogen-containing gas described in the above item. 4. After performing the dry etching process by generating reactive plasma of the halogen-containing gas and causing the reactive plasma to act on the material to be processed on the support electrode, 4. The high frequency discharge according to claim 3, wherein the high frequency voltage is applied between a counter electrode disposed near the support electrode and the high frequency voltage in a region different from the reactive plasma generation region. Processing method using a halogen-containing gas. 5. The processing method using a halogen-containing gas according to claim 4, wherein the counter electrode is grounded. 6. A reactive plasma of the halogen-containing gas is generated between a support electrode of the material to be processed and a counter electrode disposed to face the support electrode, and the reactive plasma is generated by the reactive plasma. After performing the dry etching by acting on a processing material, applying the high-frequency voltage only to the support electrode, between the counter electrode and the support electrode, substantially the support electrode The method according to claim 3, wherein the high-frequency discharge is generated only in the vicinity. 7. The processing method using a halogen-containing gas according to claim 1, wherein the dehalogenating gas is at least one gas selected from the group consisting of oxygen gas, nitrogen gas, hydrogen gas, and inert gas. . 8. The processing method using a halogen-containing gas according to claim 1, wherein reactive plasma for the processing is generated by microwaves from a magnetron. 9. The processing method using a halogen-containing gas according to claim 1, wherein a reactive plasma for the processing is generated by a high-frequency voltage applied to the inductive coupling coil. 10. The processing method using a halogen-containing gas according to claim 1, wherein a reactive plasma for the processing is generated by an interaction between the helicon wave and the electrons. 11. The processing method using a halogen-containing gas according to claim 1, wherein a reactive plasma for the processing is generated by a high-frequency voltage applied between the material to be processed and a counter electrode. 12. The processing with a halogen-containing gas according to claim 1, wherein, when the processing is performed while supporting the material to be processed by an electrostatic chuck, the discharge energy also removes a residual charge at the time of the electrostatic chuck. Method. 13. The processing method using a halogen-containing gas according to claim 2, wherein the dry etching is performed on a predetermined film formed on the semiconductor substrate. 14. A predetermined processing chamber, a first gas introduction chamber for introducing a halogen-containing gas into the processing chamber to perform predetermined processing on a material to be processed, and a dehalogenating gas in the processing chamber. In the presence of a gas for use, substantially apply the discharge energy only to the material to be treated,
An apparatus for processing with a halogen-containing gas, comprising: discharge means for removing halogen present in the material to be processed; and second gas introduction means for introducing the gas for halogen removal into the processing chamber. 15. After dry-etching a material to be processed into a predetermined fine pattern using the halogen-containing gas in the processing chamber, in the processing chamber in the presence of the dehalogenating gas, 15. The processing apparatus using a halogen-containing gas according to claim 14, wherein the high-frequency discharge energy is applied substantially only to the material to be processed to remove halogen attached to the material to be processed. 16. An electrode is disposed on the material to be processed, and between the electrode and an electrode disposed near the material to be processed.
The processing apparatus according to claim 15, wherein the high-frequency voltage is applied to generate the high-frequency discharge. 17. The method according to claim 17, further comprising: generating a reactive plasma of the halogen-containing gas, and performing the dry etching process by causing the reactive plasma to act on the material to be processed on the support electrode. The high-frequency voltage is applied between a counter electrode disposed in the vicinity of the support electrode, and the high-frequency discharge is generated in a region different from a region where the reactive plasma is generated. Item 18. A processing apparatus using a halogen-containing gas according to Item 16. 18. The method according to claim 1, wherein said counter electrode is grounded.
7. A processing apparatus using a halogen-containing gas described in 7. 19. A reactive plasma of the halogen-containing gas is generated between a supporting electrode of the material to be processed and a counter electrode disposed to face the supporting electrode, and the reactive plasma is generated by the reactive plasma. After performing the dry etching by acting on a processing material, applying the high-frequency voltage only to the support electrode, between the counter electrode and the support electrode, substantially the support electrode 17. The processing apparatus according to claim 16, wherein the high-frequency discharge is generated only in the vicinity. 20. The dehalogenating gas is an oxygen gas,
The processing apparatus using a halogen-containing gas according to claim 14, which is at least one kind of gas selected from the group consisting of nitrogen gas, hydrogen gas, and inert gas. 21. The processing apparatus according to claim 14, wherein a reactive plasma for the processing is generated by a microwave from a magnetron. 22. The processing apparatus according to claim 14, wherein a reactive plasma for the processing is generated by a high-frequency voltage applied to the inductive coupling coil. 23. The processing apparatus according to claim 14, wherein a reactive plasma for the processing is generated by an interaction between the helicon wave and the electrons. 24. The processing apparatus according to claim 14, wherein a reactive plasma for the processing is generated by a high-frequency voltage applied between the material to be processed and a counter electrode. 25. When the processing is performed while the material to be processed is supported by an electrostatic chuck, residual charge at the time of the electrostatic chuck is also removed by the discharge energy.
A processing apparatus using the halogen-containing gas according to claim 14. 26. The processing apparatus using a halogen-containing gas according to claim 15, wherein the dry etching is performed on a predetermined film formed on a semiconductor substrate.