CN1663030A - Plasma processing method - Google Patents

Abstract

A plasma processing method comprises the following steps: preparing a subject having an organic layer on a surface thereof; and irradiating H to the object to be processed₂The plasma of (3) improves the plasma resistance of the organic layer.

Description

Plasma treatment method

technical field

The present invention relates to a plasma processing method performed in a semiconductor device manufacturing process.

Background technique

A resist mask such as photoresist is used when the layer to be etched is plasma-etched. Especially recently, in response to requests for microfabrication, it is preferable to use ArF photoresist or F2 photoresist suitable for forming an opening pattern of about 0.13 μm or less, that is, a photoresist exposed by a laser using ArF gas or F2 gas as a light source. Photoresist.

However, since the ArF resist layer or the F2 resist layer has low plasma resistance, there is a problem that the surface of the resist layer becomes rough during etching. Since the surface of the photoresist layer is rough, the shape of the opening changes as the etching proceeds, so that an etched hole or etched groove of a designed shape cannot be formed. In addition, in the middle of etching, parts that do not constitute the photoresist layer are etched, and parts that are not intended to be etched are also etched.

As a method of improving the plasma resistance of the photoresist layer, there is a method of irradiating ultraviolet rays, electron beams, or ion beams to the surface of the photoresist layer (JP-A-60-110124, JP-A-2-252233, JP-A 57-157523 publication), a method of heating and curing photoresist (JP-A-4-23425 publication), or applying a thin cured layer on the surface of the photoresist layer after providing heat or light energy to the organic Si compound method (JP-A-2-40914).

In the above method of improving the plasma resistance of the photoresist layer, it is necessary to perform the treatment for improving the plasma resistance in a container different from the container used in the subsequent etching step. Transferring the object to be processed from the container for improving the plasma resistance of the photoresist layer to the etching container results in a reduction in yield in the transfer process or a reduction in productivity due to transfer time. In addition, installing a container for improving plasma resistance outside the etching container not only requires extra space, but also leads to an increase in cost.

In addition, it is also possible to add an ultraviolet irradiation unit or a heating unit to the etching vessel without providing a vessel for performing plasma resistance improvement treatment outside the etching vessel. Costs rise.

On the other hand, if the portion to be etched is directly covered with the photoresist layer, the design dimensional accuracy of the opening pattern will be lowered in the subsequent step of exposing and developing the photoresist layer to form the opening pattern. Therefore, an antireflection layer is inserted between the portion to be etched and the resist mask layer. It is proposed to use plasma containing a substance having C and F, such as a mixed gas of C ₄ F ₈ and O ₂ , a mixed gas of HBr and CF ₄ and He, a mixed gas of CH ₂ F ₂ and CF ₄ and He This antireflection layer was etched (JP-A-10-26162). As an etching gas for etching the antireflection layer, for example, a mixed gas of CF ₄ and O ₂ is also known (JP-A-7-307328).

However, when the antireflection layer is etched with plasma of a mixed gas of C ₄ F ₈ and O ₂ or a mixed gas of CF ₄ and O ₂ , the surface of the ArF photoresist layer is rough, and the ArF photoresist layer The vertical ribs are formed in the middle, and the ArF photoresist layer used as the mask layer is etched by a considerable amount, and the function as a mask cannot be realized.

Contents of the invention

The object of the present invention is to provide a kind of plasma treatment method, can improve the etching resistance of the organic layer such as ArF photoresist layer without causing yield drop or productivity drop, can not cause cost increase.

In addition, there is provided a plasma processing method that can perform plasma etching while thus improving the etching resistance of an organic layer.

In addition, a plasma treatment method is provided which can maintain high plasma resistance of mask layers such as an ArF resist layer or an F2 resist layer when etching an antireflection layer or a layer to be etched at its bottom. .

And, provide a kind of plasma treatment method, while suppressing the surface roughness of mask layers such as ArF photoresist layer or F2 photoresist layer, maintain good etching selectivity ratio, and can etch the bottom part at a large etching rate. Anti-reflection layer or etch object layer.

According to a first aspect of the present invention, there is provided a plasma treatment method comprising the steps of: preparing an object to be processed having an _organic layer on its surface; Improved plasma resistance.

According to a second aspect of the present invention, there is provided a plasma processing method comprising the steps of: preparing an object to be processed having an organic layer on its surface; and irradiating the object to be processed with plasma containing _H2 and a processing gas of an inert gas , so that the plasma resistance of the organic layer is improved.

According to a third aspect of the present invention, there is provided a plasma processing method comprising the steps of: preparing an object to be processed having an organic layer on its surface; and irradiating the object to be processed with a processing gas containing a substance having H and an inert gas. plasma, so that the plasma resistance of the organic layer is improved.

According to the 4th aspect of the present invention, a kind of plasma processing method is provided, has the following steps: prepare the object to be processed with a photoresist layer made of ArF photoresist or F2 photoresist on the surface; The body is irradiated with plasma of a processing gas containing a substance containing H to improve the plasma resistance of the photoresist layer.

According to a fifth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed in a processing container, the object to be processed having a part to be etched, and an opening pattern covering the part to be etched and forming an opening pattern. an organic layer; plasmaizing a processing gas containing a substance having H in the processing container, irradiating the plasma to the organic layer; and plasmating an etching gas in the processing container, passing through the opening pattern, The etching target portion is etched.

According to the 6th aspect of the present invention, a kind of plasma processing method is provided, has the following steps: prepare the object to be processed with a photoresist layer made of ArF photoresist or F2 photoresist on the surface; The plasma of the process gas containing a substance containing N is irradiated to improve the plasma resistance of the photoresist.

According to a seventh aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a portion to be etched, an antireflection layer covering the portion to be etched, and Covering the anti-reflection layer and forming a photoresist layer made of ArF photoresist or F2 photoresist with an opening pattern; introducing a processing gas into the processing container; plasmaizing the processing gas; and making the plasma The anti-reflection layer is etched through the opening pattern while improving the plasma resistance of the photoresist layer by acting on the object to be processed.

According to an eighth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a layer to be etched, an antireflection layer covering the layer to be etched, and Covering the anti-reflection layer and forming a mask layer with an opening pattern; introducing a processing gas containing _H into the processing container; plasmating the processing gas; and passing through the opening pattern of the mask layer, by the The plasma selectively etches the antireflection layer relative to the mask layer.

According to a ninth aspect of the present invention, there is provided a plasma processing method, which has the following steps: loading an object to be processed on a loading table, the object to be processed has a layer to be etched and a mask layer, and the mask layer covers the etched The target layer is formed with an opening pattern and is composed of ArF photoresist or F2 photoresist; in the initial etching process, plasma _CF4 and _H2 , through the opening pattern of the mask layer, etch the etching target layer to In the middle; and a main etching step, after the initial etching step, an etching gas containing a fluorocarbon is plasmatized, and the etching target layer is etched.

According to a tenth aspect of the present invention, there is provided a plasma processing method comprising the steps of loading an object to be processed, the object to be processed having a layer to be etched, an antireflection layer covering the layer to be etched, and A mask layer, the mask layer covers the anti-reflection layer and is formed with an opening pattern, which is made of acrylic resin; the first etching process is to plasmaize CF ₄ , and etch the anti-reflection layer through the opening pattern of the mask layer layer; the second etching process, plasma _CF4 and _H2 , through the opening pattern of the mask layer, etch the etching target layer to the middle; and the third etching process, after the second etching process, plasma The etching gas containing fluorocarbon is condensed, and the etching target layer is etched.

According to an eleventh aspect of the present invention, there is provided a plasma processing method comprising the steps of loading an object to be processed, the object to be processed having a portion to be etched, and covering the etched portion on a susceptor arranged in a processing container. The object layer, the mask layer with openings are formed; the processing gas containing _H is introduced into the processing container; the high-frequency power with a frequency above 100 MHz and the high-frequency power with a frequency above 3 MHz are provided to the susceptor; and the The pressure in the processing container drops below 13.3Pa (100mTorr).

According to a twelfth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed in a processing container, the object to be processed having a portion to be etched and a photoresist layer, the photoresist layer The portion to be etched is covered with an opening pattern formed of ArF photoresist or F2 photoresist; a processing gas containing a substance containing N is plasmatized in the processing container, and irradiated to the photoresist layer and plasmatizing an etching gas in the processing container to etch the etching target portion through the opening pattern.

According to a thirteenth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a portion to be etched, an antireflection layer covering the portion to be etched, and a photoresist layer, the photoresist layer covers the anti-reflection layer to form an opening pattern, and is composed of ArF photoresist or F2 photoresist; the first etching process includes plasmaization in the processing container containing N The processing gas of the substance, and through the opening pattern, etch the anti-reflection layer; and the second etching step, the etching gas is plasmaized in the processing container, and the etching target part is etched through the opening pattern .

According to a fourteenth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed in a processing container, the object to be processed having a layer to be etched and an organic mask layer, the organic mask layer The layer to be etched is covered to form an opening pattern, and the processing container is equipped with a component having an exposed portion of a substance containing Si; at least one selected from the group consisting of H ₂ , N ₂ and He is introduced into the processing container. a processing gas; and plasma the processing gas, plasma processing the organic mask layer.

According to a fifteenth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a layer to be etched, an organic film covering the layer to be etched, and an organic mask layer covering the organic film and forming an opening pattern, the processing container is equipped with components having exposed portions of a substance containing Si; introducing an etching gas into the processing container; plasma Thinning the etching gas, etching the organic film through the opening pattern of the organic mask layer; introducing at least one processing gas selected from the group consisting of H ₂ , N ₂ and He into the processing container; and plasmating the processing gas, plasma processing the organic mask layer.

According to a sixteenth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a layer to be etched, an organic film covering the layer to be etched, and an organic mask layer covering the organic film and forming an opening pattern, the processing container is equipped with a constituent member having an exposed portion of a substance containing Si; introducing _H2 into the processing container; and plasma The introduced H ₂ is condensed to etch the organic film through the opening pattern of the organic mask layer.

According to a seventeenth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed in a processing container, the object to be processed having a layer to be etched and a photoresist layer, the photoresist layer Covering the etching target layer to form an opening pattern, which is composed of ArF photoresist or F2 photoresist; introducing a processing gas containing _C2F4 into a processing container _containing the object to be processed; plasmating the processing gas and etching the etching target layer in the object to be processed by the plasma of the processing gas through the opening pattern of the photoresist layer.

According to an eighteenth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed in a processing container, the object to be processed having a layer to be etched and a mask layer covering the Etching the target layer to form an opening pattern; introducing a processing gas containing C ₂ F ₄ and O ₂ into a processing container containing the object to be processed; plasmating the processing gas; and passing through the opening of the mask layer pattern, and the etching target layer in the object to be processed is etched by the plasma of the processing gas.

According to a nineteenth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a portion to be etched, an antireflection layer covering the portion to be etched, and a photoresist layer, the photoresist layer covers the anti-reflection layer, and is formed with an opening pattern, which is made of ArF photoresist or F2 photoresist; in the processing container, the plasma is composed of substances having C and F etching the antireflection layer through the opening pattern with an etching gas having a substance of H; and etching the etching target portion.

According to a twentieth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a portion to be etched, an antireflection layer covering the portion to be etched, and a mask layer, the mask layer covers the anti-reflection layer to form an opening pattern; in the processing container, the etching gas containing substances having C and F and hydrocarbons is plasmaized, and etched through the opening pattern the antireflection layer; and etching the etching target portion.

According to a twenty-first aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a portion to be etched, and an antireflection layer covering the portion to be etched, in a processing container. , and a mask layer, the mask layer covers the anti-reflection layer, forming an opening pattern; plasma etching gas in the processing container, the etching gas contains C and F substances, and C, H and F, and a substance in which the ratio of the atomic number of H to the atomic number of F is 3 or more, the antireflection layer is etched through the opening pattern; and the etching target portion is etched.

According to a twenty-second aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed in a processing container, the object to be processed having a portion to be etched and a photoresist layer, the photoresist A layer covering the etching target portion forms an opening pattern, and is composed of ArF photoresist or F2 photoresist; in the processing container, the processing gas containing the substance having C and F and CO is plasmatized, and is supplied to the photoresist The glue layer is irradiated with the plasma, and the etching gas is plasmaized in the processing container, and the etching target portion is etched by the plasma through the opening pattern.

According to a twenty-third aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a portion to be etched, and an antireflection layer covering the portion to be etched, in a processing container. , and a photoresist layer, the photoresist layer covers the anti-reflection layer to form an opening pattern, and is made of ArF photoresist or F2 photoresist; the first etching process includes plasmaization in the processing container with The substance of C and F and the first etching gas of CO, through the opening pattern, the anti-reflection layer is etched by the plasma; and the second etching process, the second etching gas is plasmaized in the processing container , the etching target portion is etched by the plasma through the opening pattern.

According to a twenty-fourth aspect of the present invention, there is provided a plasma processing method comprising the steps of disposing an object to be processed, the object to be processed having a portion to be etched, an antireflection layer covering the portion to be etched, and a mask layer, the mask layer covers the anti-reflection layer, and an opening pattern is formed; the first etching process is to plasmaize the first etching gas comprising CF ₄ and CO in the processing container, and pass through the opening pattern , etching the anti-reflection layer by the plasma; and a second etching step of plasmating a second etching gas in the processing container, and etching the etching target portion by the plasma through the opening pattern .

According to a twenty-fifth aspect of the present invention, there is provided a plasma processing method comprising the steps of arranging an object to be processed, the object to be processed having a layer to be etched, and an organic anti-reflective coating covering the layer to be etched, in a processing container. layer, and a photoresist layer, the photoresist layer covers the organic anti-reflection layer, and is formed with an opening pattern, and is made of ArF photoresist or F2 photoresist; Introduce the etching material containing Si into the processing container gas; and plasma the etching gas to etch the organic anti-reflection layer through the opening pattern of the photoresist layer.

According to a twenty-sixth aspect of the present invention, there is provided a plasma processing method comprising the steps of loading an object to be processed on a susceptor in a processing container, the object to be processed having a portion to be etched, and covering the etched an object layer, a mask layer having an opening; an inert gas is introduced into the processing container under the object to be processed and at least a part of the surface of which is Si in the processing container; an inert gas is introduced into the processing container providing high-frequency energy that ionizes at least a portion of the inert gas; introducing an etching gas into the processing container; plasmating the etching gas; in the processing container, through the opening pattern of the mask layer, by The plasma of the etching gas etches the layer to be etched.

According to a twenty-seventh aspect of the present invention, there is provided a plasma processing method comprising the steps of loading an object to be processed, the object to be processed having a layer to be etched and a mask layer, on a susceptor located in a processing container, The mask layer covers the etching target layer to form an opening pattern; in the processing container, a Si-containing layer is formed on the surface of the mask layer; an etching gas is introduced into the processing container; gas; and the etching target layer is etched by plasma of the etching gas through the opening pattern of the mask layer in the processing container.

According to a twenty-eighth aspect of the present invention, there is provided a plasma processing method comprising the steps of: preparing a processing container, arranging therein a member whose surface is at least partly made of Si, a first electrode, and an electrode located opposite to the first electrode. The second electrode at the position; the object to be processed is loaded on the first electrode in the processing container, the object to be processed has an etching target layer and a mask layer, and the mask layer covers the etching target layer, forming a opening pattern; introducing an inert gas into the processing container; applying high-frequency power to the first electrode; applying high-frequency power to the second electrode; introducing etching gas into the processing container; In this method, the etching target layer is etched by the etching gas plasmaized by the high-frequency power through the opening pattern of the mask layer.

According to a twenty-ninth aspect of the present invention, there is provided a plasma processing method comprising the steps of loading an object to be processed, the object to be processed having a layer to be etched, and a photoresist, on a susceptor located in a processing container. layer, the photoresist layer covers the etching target layer, forming an opening pattern, and is composed of ArF photoresist or F2 photoresist; introducing an etching gas containing a Si compound into the processing container; plasmating the etching gas and in the processing vessel, the etching target layer is etched by the plasma of the etching gas through the opening pattern of the photoresist layer.

Description of drawings

FIG. 1 is a cross-sectional view showing an example of a plasma processing apparatus capable of implementing the plasma processing method of the present invention.

2 is a cross-sectional view showing another example of a plasma processing apparatus capable of implementing the plasma processing method of the present invention.

Fig. 3 is a cross-sectional view schematically showing an object to be processed used in the implementation of Embodiment 1 of the present invention.

4A and 4B are cross-sectional views schematically showing the state of an object to be processed used in the implementation of Embodiment 2 of the present invention in the order of steps.

5A and 5B are cross-sectional views schematically showing the state of an object to be processed used in the implementation of Embodiment 3 of the present invention in the order of steps.

6A, 6B, and 6C are cross-sectional views schematically showing the state of an object to be processed used in the implementation of Embodiment 4 of the present invention in the order of steps.

7A, 7B, and 7C are cross-sectional views schematically showing the state of an object to be processed used in the implementation of Embodiment 5 of the present invention in the order of steps.

Fig. 8 is a flow chart showing a series of steps in Embodiment 5 of the present invention.

9A, 9B, and 9C are cross-sectional views schematically showing the state of an object to be processed used in the implementation of a modified example of Embodiment 5 of the present invention in the order of steps.

Fig. 10 is a flow chart showing a series of steps in a modified example of Embodiment 5 of the present invention.

11A and 11B are graphs showing the effect of plasma treatment in Examples of Embodiment 5 of the present invention.

Fig. 12 is a cross-sectional view schematically showing an object to be processed used in the implementation of Embodiment 6 of the present invention.

13A and 13B are cross-sectional views schematically showing the state of an object to be processed used in the implementation of Embodiment 7 of the present invention in the order of steps.

14A and 14B are cross-sectional views schematically showing the state of an object to be processed used in the implementation of the eighth embodiment of the present invention in the order of steps.

Fig. 15 is a cross-sectional view schematically showing an object to be processed used in the implementation of Embodiment 9 of the present invention.

16A and 16B are cross-sectional views schematically showing the state of an object to be processed used in the implementation of Embodiment 10 of the present invention in the order of steps.

Detailed ways

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a cross-sectional view showing an example of a plasma processing apparatus capable of implementing the plasma processing method of the present invention.

The plasma processing apparatus 1 has a processing container 2 . The processing container 2 is made of metal, such as aluminum with an oxidized surface, and is safely grounded. At the bottom inside the processing container 2, via the insulator 3, a base 5 serving as a lower electrode of a parallel plate electrode is provided. A high-pass filter (HPF) 6 is connected to the base 5 , and a second high-frequency power supply 50 is connected via a matching unit 51 . An electrostatic chuck 11 is provided on the susceptor 5, and an object W to be processed, such as a semiconductor wafer, is placed thereon.

The electrostatic chuck 11 is configured to sandwich an electrode 12 between insulators, and electrostatically attracts the object W to be processed by applying a DC voltage from a DC power supply 13 connected to the electrode 12 . In addition, the focus ring 15 made of alumina, Si, SiO ₂ , etc. is arranged to surround the object W to be processed, so that the uniformity of etching is improved.

In addition, above the susceptor 5 , facing the susceptor 5 , a showerhead-shaped upper electrode plate 24 made of Si, SiO ₂ , amorphous carbon, or the like is supported by a support body 25 . The upper electrode 21 of the parallel plate electrode facing the susceptor 5 is constituted by the upper electrode plate 24 and the support body 25 . A low-pass filter 42 is connected to the upper electrode 21 , and a first high-frequency power supply 40 is connected via a matching unit 41 .

A gas inlet 26 is provided at the center of the upper electrode 21, and a gas supply pipe 27 is connected to the gas inlet 26. A valve 28 and a mass flow controller 29 are sequentially connected to the gas supply pipe 27 from the side of the gas inlet 26. . The processing gas supply source 30 . A predetermined processing gas is supplied from the processing gas supply source 30 .

On the other hand, an exhaust pipe 31 is connected to the bottom of the processing container 2 , and an exhaust device 35 is connected to the exhaust pipe 31 . In addition, a gate valve 32 is provided on the side wall of the processing container 2, and the object W to be processed is conveyed between the adjacent load lock chamber (not shown).

In the apparatus configured in this way, first, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Thereafter, the gate valve 32 is closed, and after the pressure in the processing container 2 is decompressed by the exhaust device 35, the valve 28 is opened, and a predetermined processing gas is supplied from the etching gas supply source 30, so that the pressure in the processing container 2 becomes a predetermined value. value.

In this state, high-frequency power is supplied from the first and second high-frequency power sources 40 and 50 to plasmatize the processing gas, and plasma treatment (plasma resistance improvement treatment or plasma treatment) is performed on a predetermined film of the object W to be processed. body etching). At this time, before and after the timing at which high-frequency power is supplied from the first and second high-frequency power sources 40 and 50, a DC voltage is applied to the electrodes 12 in the electrostatic chuck 11 to electrostatically adsorb the object W to be processed on the electrostatic chuck 11. In this state, predetermined plasma processing is performed.

Fig. 2 is a cross-sectional view showing another example of a plasma processing apparatus embodying the present invention.

This plasma etching device 61 has a processing container 62 . The processing container 62 is formed into a segmented cylindrical shape composed of a small-diameter upper portion 62a and a large-diameter lower portion 62b, is made of metal such as aluminum with an oxidized surface, and is grounded. At the bottom of the processing container 62, a conductive material serving as a lower electrode of the parallel plate electrode, for example, a susceptor 65 made of oxidized aluminum on the surface is provided via an insulator 63. An electrostatic chuck 71 is provided on the susceptor 65, and an object W to be processed, such as a semiconductor wafer, is placed thereon.

The electrostatic chuck 71 is configured to sandwich an electrode 72 between insulators, and electrostatically attracts the object W to be processed by applying a DC power supply 73 connected to the electrode 72 . In addition, a focus ring 75 made of Si, SiO _{2 ,} etc. is arranged to surround the object W to be processed, so that the uniformity of etching is improved.

Further, above the susceptor 65 , facing the susceptor 65 , a showerhead-shaped upper electrode plate 81 made of Si or the like is supported on the upper portion 62 a of the processing container 62 . The processing container 62 also serves as a parallel plate-type electrode facing the susceptor. Around the upper portion 62a of the processing container 62, a multi-polarized magnet 82 is rotatably provided.

A gas inlet 86 is provided at the center of the upper surface of the processing container 62, and a gas supply pipe 87 is connected to the gas inlet 86. A valve 88 and a mass flow controller 89 are sequentially connected to the gas supply pipe 87 from the side of the gas inlet 86. . The processing gas supply source 90 . A predetermined processing gas is supplied from the processing gas supply source 90 .

On the other hand, an exhaust pipe 91 is connected to the bottom of the processing container 62 , and an exhaust device 95 is connected to the exhaust pipe 91 . In addition, a gate valve (not shown) is provided on the side wall of the processing container 62, and the object W to be processed is conveyed between the adjacent load lock chamber (not shown).

A first high-frequency power source 101 and a second high-frequency power source 102 are connected to the base 65 as a lower electrode via a matching unit 100 . The frequencies of the first and second high-frequency power sources 101 and 102 are, for example, 100 MHz and 3.2 MHz, respectively.

In the apparatus configured in this way, first, the gate valve (not shown) is opened, and the object W to be processed is carried into the processing container 62 and placed on the electrostatic chuck 71 . Thereafter, the gate valve is closed, and after the pressure in the processing container 62 is decompressed by the exhaust device 95, the valve 88 is opened, and a predetermined processing gas is supplied from the etching gas supply source 90, so that the pressure in the processing container 62 becomes a predetermined value. .

In this state, high-frequency power is supplied from the first and second high-frequency power sources 101 and 102 to plasmatize the processing gas, and plasma treatment (plasma resistance improvement treatment or plasma treatment) is performed on a predetermined film of the object W to be processed. body etching). At this time, before and after the timing at which high-frequency power is supplied from the first and second high-frequency power sources 101 and 102, a direct current voltage is applied to the electrode 72 in the electrostatic chuck 71 to electrostatically adsorb the object W to be processed on the electrostatic chuck 71. In this state, predetermined plasma processing is performed.

Next, an embodiment of the plasma processing method of the present invention will be described.

(Embodiment 1)

Here, with the plasma processing apparatus 1 shown in FIG. 1, the following steps are carried out: plasma is irradiated to the object _W to be processed, as shown in FIG. Layer 122, the photoresist layer is a mask layer covering _SiO2 film 121, made of ArF photoresist or F2 photoresist, so that the plasma resistance of photoresist layer 122 is improved; after this process, the The photoresist layer 122 is used as a mask, and the layer 121 to be etched is plasma etched.

As the ArF resist or F2 resist, alicyclic-containing acrylic resin, cycloolefin resin, cycloolefin-anhydrous maleic acid resin, methacrylic resin, etc. can be used.

First, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Next, the gate valve 32 is closed, and after the pressure in the processing container 2 is depressurized by the exhaust device 35, the valve 28 is opened, and a processing gas, such as H ₂ , is supplied from the processing gas supply source 30, and the pressure in the processing container 2 is reduced. As a predetermined value, it is preferably 13.3 Pa (100 mTorr) or less, for example, 6.7 Pa (50 mTorr). In this state, high-frequency power is applied to the upper electrode 21 and the susceptor 5 serving as the lower electrode to plasmatize the processing gas, and the plasma irradiates the photoresist layer 122 in the object W to be processed. At this time, before and after the timing of applying high-frequency power to the upper and lower electrodes, DC power 13 is applied to electrodes 12 in electrostatic chuck 11 to electrostatically adsorb object W to electrostatic chuck 11 .

Instead of plasma of _H2 , plasma of processing gas containing _H2 and inert gases such as He, Ne, Ar, Kr, and Xe, or plasma of other substances containing H, or plasma containing substances containing H and other substances can be irradiated. A plasma of a process gas of a substance, such as an inert gas. As another H-containing substance, for example NH ₃ . Irradiation of these gases improves the plasma resistance of the photoresist layer 122 which is an organic layer. Although the detailed mechanism is not necessarily clear, it is considered that the plasma containing H promotes the crosslinking reaction of the photoresist layer 122 which is an organic layer, and the CO bond or CH bond becomes CC bond, thereby strengthening the chemical bond and improving the plasma resistance. As a substance having H, the above-mentioned H ₂ or NH ₃ is preferable in terms of ease of handling. NH ₃ is also a substance having N, but as the process gas, other substances having N, such as N ₂ , may be used. _N2 also has the advantage of being easy to handle. Since the plasma resistance of the photoresist layer 122 is improved by using a substance containing N as the process gas, a substance containing N may be used instead of a substance containing H. At this time, the detailed mechanism of the improvement of plasma resistance may not be clear, but it is believed that N bonds with C in the ArF photoresist to form a CN-based protective film on the surface of the ArF photoresist layer, and the plasma resistance of the ArF photoresist improve. When a substance having N such as N ₂ is contained in the processing gas, it is preferable to further contain a substance having H. This is because the bonding of N and C is considered to be promoted by the presence of H. As the substance having H, one or more selected from H ₂ , CHF ₃ , CH ₂ F ₂ , and CH ₃ F can be used.

After the plasma is irradiated for a prescribed time as described above, the supply of process gas and the application of high-frequency power are stopped.

Thereafter, the pressure in the processing container 2 is changed to a predetermined value suitable for the etching process, for example, 2.0 Pa (15 mTorr), and an etching gas is supplied from the processing gas supply source 30 . As the etching gas, a gas containing fluorocarbons such as C ₅ F ₈ is preferable. As a specific example, for example, C ₅ F ₈ +O ₂ +Ar. The part to be etched is a _SiO2 layer, and when the etching gas is a gas containing _C5F8 , the selectivity of _{the SiO2} film 121 as the part to be etched to the photoresist layer 122 as an organic layer (the part to be etched The etching rate/etching rate of the organic layer) is high. Among C ₅ F ₈ , it is preferable to select a relatively high straight-chain C ₅ F ₈ , in which 1,1,1,4,4,5,5,5-octafluoro-2 pentyne (hereinafter referred to as "2-C ₅ F ₈ "."), the above selection ratio is very large. In addition, it is preferable to contain C ₄ F ₆ as the etching gas. By using C ₄ F ₆ , the polymer is deposited on the ArF photoresist in the etching process, so that the photoresist is not lost, and the desired opening shape can be maintained to form an etched hole.

While flowing the etching gas in this way, high-frequency power is applied to the upper electrode 21 and the susceptor 5 serving as the lower electrode, the etching gas is plasmatized, and the photoresist layer 122 is used as a mask, and _SiO2 is etched by the plasma. Film 121.

During etching, an end point detector (not shown) detects a predetermined luminescence intensity, and the etching is terminated accordingly.

In addition, the etching target part is not limited to the _SiO2 film, and can also be applied to oxide films (oxygen compounds) such as TEOS, BPSG, PSG, SOG, thermal oxide films, HTO, FSG, organic Si oxide films, and CORAL (Noberas Corporation). Or etching of low-dielectric organic insulating films, etc. At this time, since the material of the portion to be etched is different, a gas obtained by adding other gases to the processing gas may be used as the etching gas. If etching can be performed only by adding another gas after the step of irradiating the plasma of the processing gas in this way, the step of irradiating the plasma of the processing gas and the etching step can be continuously performed while maintaining the plasma discharge. As a specific example, for example, in the process of irradiating the plasma of the processing gas, H ₂ is used as the processing gas, and thereafter, a mixed gas of H ₂ , CF ₄ and Ar is used as the etching gas, and the etching target portion such as etching organic oxide film.

In addition, it is not limited to photoresist materials with low plasma resistance such as ArF photoresist or F2 photoresist, and other organic photoresist layers can also be used instead, and it is not limited to photoresist, and other organic photoresist layers can also be used. layer. The structure of the plasma processing apparatus is also not limited to that shown in FIG. 1 .

Next, an example of the method of the above-mentioned first embodiment will be described.

Here, as each condition of the plasma irradiation process, the pressure in the processing container is set to 6.7 Pa (50 mTorr), the flow rate of the processing gas _H is set to 0.05-0.2 L/min (50-200 sccm), and the irradiation time is set to For 30 seconds, apply high-frequency power with a frequency of 60 MHz to the upper electrode with a power of 500-1000 W, and do not apply high-frequency power to the lower electrode. In addition, as conditions in the etching process, the pressure in the processing container was set to 2.0 Pa (15 mTorr), and the flow rates of etching gases C ₅ F ₈ , Ar, and O ₂ were set to 0.015 L/min (15 sccm) and 0.38 L/min, respectively. /min (380sccm), 0.019L/min (19sccm), apply high-frequency power of 60MHz frequency to the upper electrode with a power of 2170W, and apply high-frequency power of 2MHz frequency to the lower electrode with a power of 1550W.

In such an example and a comparative example in which the plasma irradiation process was omitted, the selectivity ratio of the _SiO2 film to the ArF resist mask in the etching process (etching rate of the _SiO2 film/etching rate of the ArF resist mask rate). With respect to all four points of the measurement site of the object W to be processed, by irradiating plasma as in the example, the above-mentioned selectivity ratio increased compared to the comparative example in which no plasma was irradiated. The ascent rate is 6-19%.

(Embodiment 2)

Here, the first etching step (FIG. 4A) is implemented with the above-mentioned plasma etching apparatus 1, and the antireflection film 132 is etched through the pattern opening of the photoresist layer 133 to the object W to be processed. SiO ₂ film 131, an anti-reflection film 132 covering the SiO ₂ film 131, and a photoresist layer 133, the photoresist layer 133 covers the anti-reflection film 132, and is made of ArF photoresist or F2 photoresist, Simultaneously, the plasma resistance of the photoresist layer 133 is improved; and the second etching process (FIG. 4B), through which the photoresist layer 133 after this process, plasma-etches the _SiO2 film 131.

First, the object W to be processed is loaded and arranged in the processing container 2, and a processing gas serving as a first etching gas, such as N ₂ and H ₂ , is supplied from the processing gas supply source 30. At the same time, the pressure in the processing container 2 is changed to Specified value, such as 107Pa (800mTorr). The pressure inside the processing container at this time is preferably 107-160 Pa (800-1200 mTorr). If it is lower than 107Pa, the photoresist layer 133, especially the shoulder of the pattern opening will be etched, and if it is higher than 160Pa, the opening part will not be etched. As the processing gas that also serves as the first etching gas, a gas containing N, such as N ₂ , NH ₃ , can be used. In addition, a gas containing H, such as H ₂ , CHF ₃ , CH ₂ F ₂ , CH ₃ F One or more of the selected.

Next, high-frequency power is applied to the upper and lower electrodes to plasmatize the first etching gas, and the antireflection film 132 is etched using the photoresist layer 133 as a mask. As the antireflection film 132, amorphous carbon or an organic polymer material can be used. This etching also serves as a process for improving the plasma resistance of the photoresist layer 133 at the same time. Only after etching for a prescribed time, the first etching is ended.

By making the processing gas the same as the etching gas, gas switching between the step of irradiating the photoresist layer 133 with plasma and the step of etching the antireflection layer 132 is unnecessary, and the processing can be performed in a short time, thereby improving productivity. In addition, since the plasma resistance-improving treatment of the ArF resist can be performed when the anti-reflection layer 132 is etched, redundant equipment and space for the treatment are unnecessary.

Next, the process gas (first etching gas) is switched to an etching gas (second etching gas), and second etching of plasma etching the SiO ₂ film 131 through the photoresist 133 is performed as in the first etching. The etching gas at this time is preferably a gas containing fluorocarbons, such as C ₅ F ₈ , as in the first embodiment. As a specific example, for example, C ₅ F ₈ +O ₂ +CO+Ar. Among C ₅ F ₈ , linear C ₅ F ₈ is preferred, especially 2-C ₅ F ₈ . As the fluorocarbon used for the etching gas, C ₄ F ₆ may also be used.

In addition, in the second embodiment, the etching target part is not limited to the SiO ₂ film, and it can also be applied to TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic Si oxide film, CORAL (Noberas Corporation) Etching of oxide films (oxygen compounds) or low-dielectric organic insulating films. In addition, it is not limited to resist material with low plasma resistance such as ArF resist or F2 resist, but other organic resist layers may be used, and not limited to resist, but other organic layers may also be used. The structure of the plasma processing apparatus is also not limited to that shown in FIG. 1 .

Next, an example of the method of the above-mentioned second embodiment will be described.

Here, as each condition of the first etching, the pressure in the processing container is set to 107 Pa (800 mTorr), and the flow rates of the processing gas (first etching gas) N ₂ and H ₂ are set to 0.6 L/min (600 sccm) respectively, and A high-frequency power of 60 MHz frequency was applied to the upper electrode with a power of 1000 W, and a high-frequency power supply of a frequency of 2 MHz was applied to the lower electrode with a power of 300 W. As each condition of the second etching, the etching gas contains 1,2,3,3,4,4,5,5-octafluoro-cyclo-1-pentene (hereinafter referred to as "cC ₅ F ₈ ".) In the case of the gas (Example 2-1), the pressure in the processing container is set to 2.0Pa (15mTorr), and the flow rates of the etching gases cC ₅ F ₈ , Ar, and O ₂ are set to 0.015L/min (15 sccm) respectively. , 0.38L/min (380sccm), 0.019L/min (19sccm), apply 60MHz high-frequency power to the upper electrode with 2170W power, apply 2MHz high-frequency power to the lower electrode with 1550W power, in the etching gas In the case of a gas containing 2-C ₅ F ₈ ″ (Example 2-2), the pressure inside the processing container was set at 2.7 Pa (20 mTorr), and the etching gas 2-C ₅ F ₈ , Ar, O ₂ , The flow rate of CO was set to 0.027L/min (27sccm), 0.5L/min (500sccm), 0.027L/min (27sccm), 0.05L/min (50sccm), and a high frequency of 60MHz was applied to the upper electrode with a power of 1600W. High-frequency power, apply high-frequency power to the lower electrode with a frequency of 2MHz and a power of 2000W.

On the contrary, after the first etching was performed by the process gas of CF ₄ which is not considered to have an effect on improving the plasma resistance of the ArF resist, the second etching was performed with a gas containing cC ₅ F ₈ as in Example 2-1. The second etching is referred to as Comparative Example 2-1, and the second etching is performed with a gas containing 2-C ₅ F ₈ as in Example 2-2, which is referred to as Comparative Example 2-2. The results are shown in Table 1.

Table 1 process gas etching gas Etching rate of _SiO2 /etching rate of ArF photoresist in the second etching process Example 2-1 N ₂ +H ₂ Gases _{containing cC5F8} 8.3 Comparative example 2-1 CF ₄ Gases _{containing cC5F8} 6.3 Example 2-2 N ₂ +H ₂ Gas containing 2-C ₅ F ₈ 63.3 Comparative example 2-2 CF ₄ Gas containing 2-C ₅ F ₈ 22.5

As shown in Table 1, it was confirmed that the plasma resistance of the ArF photoresist film was improved by using the plasma of the mixed gas of _N2 and _H2 in the first etching process of etching the antireflection film, and then the SiO2 film was etched. In the second etching step of _{the 2} film, the selectivity ratio of the SiO ₂ film to the ArF resist film (etching rate of SiO ₂ /etching rate of ArF resist) becomes high.

(Embodiment 3)

Here, using the plasma etching apparatus 61 shown in FIG. 2, the following steps are carried out: on the object W to be processed, the object W to be processed has the _SiO2 film 141 as the etching target layer shown in _FIG . Anti-reflection film 142 and photoresist layer 143, this photoresist layer 143 covers this anti-reflection film 142, is made of ArF photoresist or F2 photoresist, by plasma, the anti-plasma of photoresist layer 143 is made The bulkiness is improved, and the anti-reflection film 142 is etched through the opening pattern 143a of the photoresist layer 143 (FIG _. 5A); .

In this embodiment mode, as ArF resist or F2 resist, acrylic resin containing alicyclic, cycloolefin resin, cycloolefin-anhydrous maleic acid resin can be used. As the antireflection layer, an organic polymer material or amorphous carbon can be used.

First, a gate valve (not shown) is opened, and the object W to be processed is carried into the processing container 62 and placed on the electrostatic chuck 71 . Next, close the gate valve, after depressurizing the inside of the processing container 62 by the exhaust device 95, open the valve 88, supply a processing gas, such as H ₂ , from the processing gas supply source 90, and change the pressure in the processing container 62 to specified value. The processing gas may be only H ₂ , or a diluent gas such as Ar may be added at the same flow rate as H ₂ . As the processing gas, instead of H ₂ , other substances having H may be used.

In this state, high-frequency power is supplied from the first and second high-frequency power sources 101 and 102 to make the processing gas plasma and act on the object W to be processed. At this time, the DC power supply 73 is applied to the electrodes 72 in the electrostatic chuck 71 before and after the timing of supplying high-frequency power, so that the object W to be processed is electrostatically attracted to the electrostatic chuck 71 .

As mentioned above, the plasma treatment for a predetermined time is performed to improve the plasma resistance of the photoresist layer 143, and at the same time, the anti-reflection layer 142 is etched. )the following. After lowering the pressure in this way, the photoresist layer 143 serving as the mask layer is irradiated with the plasma of the processing gas containing H to modify the surface and improve the plasma resistance of the mask layer. By improving the plasma resistance of the photoresist layer 143, when the etching target layer is plasma-etched through the opening pattern 143a of the photoresist layer 143, the selectivity ratio between the etching target layer and the mask layer, that is, can be improved. Etching rate of the etching target layer/etching rate of the mask layer. In addition, it is possible to prevent ribs or grooves from entering the photoresist layer 143 as a mask layer due to plasma in this etching step. In addition, it is possible to suppress the enlargement of the opening of the photoresist layer 143 as a mask layer. The detailed mechanism of the improvement of the plasma resistance of the photoresist layer 143 as a mask layer is not necessarily clear, but it is considered that CH is extruded from the photoresist layer by the action of the H atom group on the surface of the photoresist layer _143. and other gases, so that the chemical bonds between the carbon elements in the mask layer become stronger bonds. In addition, it is preferable that a substance having N is contained in the processing gas. This is because when a substance containing N is included in the processing gas, the protective film mainly composed of C and N will cover the side wall surface of the mask layer, and it is believed that the H atom groups that contribute to the improvement of plasma resistance will not be removed from the The sidewall surface penetrates into the inside, and the improvement of the plasma resistance of the sidewall surface of the mask layer does not extend over a thick depth. From the viewpoint of further alleviating damage to the photoresist layer 143 during processing, the processing pressure is preferably 8 to 30 mTorr.

In addition, by supplying high-frequency power for plasma formation from the first high-frequency power source 101 to the susceptor 65, the plasma resistance of the photoresist layer 143 as a mask layer can also be improved. The frequency at this time is preferably 100 MHz or higher. In addition, by supplying different high-frequency power from the second high-frequency power source 102 to the susceptor 65, preferably power with a frequency of 3 MHz or higher, active species in the plasma, especially ions, can be controlled. The different high-frequency power is preferably 100W or less. This is because damage to the photoresist layer 143 as a mask layer can be suppressed to a minimum by performing processing under a low-voltage, low-power (low bias) atmosphere. In addition, since the H atom group permeates from the side wall of the photoresist layer 143 to the inside under the atmosphere of low pressure and low power (low bias voltage), it is possible to achieve a thickness from the side wall surface of the photoresist layer 143 to the inside. The part improves plasma resistance. This is because the photoresist layer 143 is an organic material containing carbon elements, so this surface modification effect is obvious. In addition, for the ArF photoresist or F2 photoresist constituting the photoresist layer 143, since the plasma resistance changes before and after the plasma resistance improvement treatment, it is very effective to apply this treatment to microfabrication. big. In addition, since the antireflection layer 142 necessary for etching the etching target layer is etched simultaneously with this plasma resistance improvement treatment, the photoresist layer 143 as a mask layer is basically not etched, and the The antireflection layer 142 is etched.

At this time, as described above, by supplying high-frequency power with a frequency of 100 MHz or higher to the susceptor 65, the H in the processing container 62 dissociates and becomes various active species. Among the active species, H atom groups mainly contribute to Improving the plasma resistance of the photoresist layer 143 as a mask layer, mainly H radicals and ions helps to prevent the etching of the reflective layer 142 . Since the contribution of the active species is well balanced, the antireflection layer 142 can be etched efficiently while improving the plasma resistance of the photoresist layer 143 as a mask layer. Furthermore, by supplying high-frequency power from a high-frequency power supply having a frequency of 3 MHz or higher from the second high-frequency power supply 102 to the susceptor 65, the movement of ions in the active species can be controlled.

Next, an etching gas for etching the SiO ₂ film 141 which is the layer to be etched, for example, a gas containing fluorocarbons such as a mixed gas of C ₄ F ₆ with O ₂ and Ar is supplied to the above-mentioned processing gas, and from the first and the second high-frequency power supply to apply high-frequency power to the susceptor 65 to plasma the processing gas, and use the photoresist layer 143 as a mask to etch the SiO ₂ film 141 by the plasma.

During etching, an end point detector (not shown) detects a predetermined luminescence intensity, and the etching is terminated accordingly.

In addition, in this embodiment, the part to be etched is not limited to the _SiO2 film, but can also be applied to TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic Si oxide film, CORAL (Noberas Corporation), etc. Etching of oxide films (oxygen compounds) or low-dielectric organic insulating films, etc. In addition, it is not limited to photoresist materials with low plasma resistance such as ArF photoresist or F2 photoresist, but also other organic photoresist layers, and is not limited to photoresist, and can also be other mask layers. . The structure of the plasma processing apparatus is also not limited to that shown in FIG. 2 .

Next, examples based on this embodiment will be described.

Here, first, three pressures in the container were set at 1.07 Pa (8.0 mTorr), 4.00 Pa (30 mTorr), and 13.3 Pa (100 mTorr), and H ₂ was supplied as a processing gas from a processing gas supply source. The frequencies of the first and second high-frequency power supplies are respectively set to 100MHz and 3.2MHz, and their powers are set to 2400W and 500W. In addition, the case where no power was supplied from the second high-frequency power source (=0 W) was also evaluated. Evaluation was performed by observing the cross-sectional state of the mask layer with a microscope (SEM).

As a result, when the pressure was 1.07Pa (8.0mTorr) or 4.00Pa (30mTorr), there was basically no entry of ribs or grooves into the mask layer or expansion of openings. When the pressure is 13.3Pa (100mTorr), the ribs and grooves enter the mask layer or the expansion of the opening is not much. If the pressure becomes high, ribs and grooves are likely to enter.

In addition, with regard to the power supplied from the second high-frequency power supply, the entry of ribs and grooves into the mask layer or the enlargement of openings was less at 0 W than at 500 W. Considering these results and the like, the power supplied from the second high-frequency power supply is preferably 100W or less.

And, the pressure is fixed at 1.07Pa (8.0mTorr), and the flow rate of _H2 is changed to 50mL/min(sccm), 100mL/min(sccm), 120mL/min(sccm), 200mL/min(sccm), where the flow When it is small, the entry of ribs and grooves into the mask layer and the expansion of openings are small.

In the subsequent step of etching the _SiO2 film which is the layer to be etched, a mixed gas of _C4F6 , _{O2 and} Ar is used as an etching gas in the processing container, and the pressure in the processing container is set to 6.66Pa (50mTorr), The high-frequency power supplied to the base 65 from the first high-frequency power supply is 600W, and that supplied from the second high-frequency power supply is 1800W. The etching gas is plasmaized by supplying high-frequency power from the first high-frequency power source, and the _SiO2 film that is the layer to be etched is etched. After the end-point detection method etc. is used to finish etching, the results of SEM observation are also carried out. Even after the plasma etching of the etching target layer is completed, the mask layer is greatly reduced, ribs, grooves enter the mask layer, or the mask layer The expansion of the opening is not too much either. From this, it can be seen that the improvement effect of the plasma resistance of the mask layer of the present invention continues even after plasma etching of the etching target layer.

(Embodiment 4)

Here, using the plasma processing apparatus 1 shown in FIG. 1 above, the following steps are implemented: the antireflection film 152 is etched through the opening pattern of the photoresist layer 153 on the object W to be processed, which is shown in FIG. 6A . As shown, there is an _SiO2 layer 151 as an etching target layer, an antireflection layer 152 covering it, and a photoresist layer 153 which is a mask layer for forming an opening pattern 153a covering the antireflection layer 152. , consisting of ArF photoresist or F2 photoresist; and etching _SiO2 layer 151.

In this embodiment, as ArF resist or F2 resist, acrylic resin containing cycloaliphatic, cycloolefin resin, cycloolefin-anhydrous maleic acid resin can also be used. As the antireflection layer, an organic polymer material or amorphous carbon can be used.

In this embodiment, the etching process is carried out in the following three stages, that is, the first etching process, through the opening pattern 153a of the photoresist layer 153, plasma etching the antireflection film 152; the second etching process, through the photoresist layer 153 opening pattern of the resist layer 153, etching the SiO ₂ layer 151 halfway; and a third etching process, after the second etching process, also etching the SiO ₂ layer 151. Wherein, the second etching process is performed as an initial etching process of the SiO ₂ layer 151 , and the third etching process is performed as a main etching process of the SiO ₂ layer 151 .

First, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Next, the gate valve 32 is closed, the pressure in the processing container 2 is reduced by the exhaust device 35, and the valve 28 is opened to supply H ₂ from the processing gas supply source 30 to bring the pressure in the processing container 2 to a predetermined value. In this state, high-frequency power is supplied from the first and second high-frequency power sources 40 and 50, and H ₂ is plasmaized to act on the object W to be processed, and the opening pattern of the photoresist layer 153 is etched to prevent reflection. Layer 152 (first etch; Figure 6A). On the other hand, before and after the timing when high-frequency power is supplied from the first and second high-frequency power sources 40 and 50, the DC power source 13 is applied to the electrodes 12 in the electrostatic chuck 11, so that the object W to be processed is electrostatically attracted to the electrostatic chuck 11. . During etching, an end point detector (not shown) detects a predetermined luminous intensity, and the supply of high-frequency power is stopped accordingly to complete the first etching.

Next, as in the first etching process, a mixed gas of CF ₄ and H ₂ is provided in the same processing container or in other processing containers, and through the opening pattern of the photoresist layer 153, the SiO ₂ layer 151 is etched halfway (second Etching process; Figure 6B). After a predetermined etching time, for example, 60 seconds, the second etching step is terminated. After that, as in the second etching process, a gas different from the second etching process, such as a mixed gas of linear C ₅ F ₈ , O ₂ and Ar, is supplied to the same processing container or another processing container to further etch SiO ₂ Layer 151 (third etching process; FIG. 6C ). The third etching step is ended according to the endpoint detection.

In this way, through the second etching process of the SiO ₂ layer 151 using the plasma of CF ₄ and H ₂ , on the surface of the ArF photoresist layer 153 as a mask layer, especially near the boundary with the SiO ₂ layer 151, a A large protective film can suppress the shape deformation of the photoresist layer 153 in the subsequent third etching process. In addition, by etching the antireflection layer 152 using H ₂ plasma in the first etching step, the shape deformation of the photoresist layer 153 in the third etching step can be further effectively suppressed. This is considered to be because oxygen atoms are detached from the vicinity of the surface of the photoresist layer 153 as a mask layer by the H ₂ plasma to form structurally strong bonds between carbon elements.

This effect of suppressing the shape deformation of the photoresist layer 153 by the plasma is particularly remarkable when the material is a methacrylic resin (referring to a resin that adds methacrylic acid to the structure) that is easily deformed by the plasma, However, the same effect can be obtained even with other resins such as acrylic resin (resin with acrylic acid added to its structure). However, when the material of the photoresist layer is acrylic resin, it is not necessary to use _H2 in the first etching of the antireflection layer because the mask material that can be finely processed has a high deformation resistance against plasma. Gas, the anti-reflection layer 152 can be etched at a high speed using plasma of CF ₄ , which has a higher etching rate than H ₂ and has the least damage to the mask layer among fluorocarbons.

In addition, by using a gas containing linear C ₅ F ₈ and O ₂ as the etching gas in the third etching step, the SiO ₂ layer 151 which is the layer to be etched can be etched more anisotropically and at a higher speed. In addition, the etching gas in the third etching step is not limited thereto, but it is preferable to use a gas different from the mixed gas of CF ₄ and H ₂ used in the second etching step. This is because desired functions such as more anisotropic etching or more high-speed etching can be provided by switching to the etching gas used in the third etching step after forming a structure for suppressing shape deformation of the mask layer in the second etching step. From the viewpoint of etching the SiO ₂ layer 151 more anisotropically and at a higher speed, it is preferable to use a gas containing fluorocarbon as the etching gas, but the above-mentioned gas containing linear C ₅ F ₈ and O ₂ is preferable.

The above describes the etching process when the antireflection layer 152 is present. However, in the absence of the antireflection layer, the above-mentioned first etching process is omitted, and the initial etching process is first performed to plasmaize _CF4 and _H2 , and pass through the ArF photoresist. The opening pattern of the layer, etch the _SiO2 layer as the etching target layer to the middle, after the initial etching process, implement the main etching process, plasmaization preferably contains fluorocarbon etching gas, preferably the above-mentioned linear C ₅ F ₈ and _O2 gas, and etch the remaining part of the _SiO2 layer as the etching target layer. At this time, on the surface of the ArF photoresist layer as the mask layer, especially in the vicinity of the interface with the _SiO2 layer as the etching target layer, a large number of protective films are formed, which can suppress the ArF light in the subsequent main etching process. The shape of the resist layer is deformed.

In addition, in this embodiment, the part to be etched is not limited to the _SiO2 film, and it is also applicable to TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic Si oxide film, CORAL (Noberas Corporation), etc. Etching of oxide films (oxygen compounds) or low-dielectric organic insulating films. In addition, it is not limited to photoresist materials with low plasma resistance such as ArF photoresist or F2 photoresist, and other organic photoresist layers can also be used instead, and it is not limited to photoresist, and other masks can also be used. mold layer. The structure of the plasma processing apparatus is also not limited to that shown in FIG. 1 .

Next, examples based on this embodiment will be described.

For the antireflection layer 152 of the object to be processed shown in FIG. 6A and the SiO ₂ layer 151 as an etching target layer, etching No. 1-6 under the conditions shown in Table 2 was performed using the apparatus shown in FIG. 1 . In addition, for any etching, the frequency of the first high-frequency power supply was set to 60 MHz, and the frequency of the second high-frequency power supply was set to 2 MHz.

Specifically, No.1-3 uses the ArF photoresist of acrylic resin as the photoresist layer 153, and the third etching process of each uses C ₄ F ₆ and O ₂ and Ar, wherein No.1 is in CF ₄ was used in the first etching process, the second etching process was not performed, No. 2 used CF ₄ in the first etching process, CF ₄ and H ₂ were used in the second etching process, No. 3 was used in the first etching process H ₂ is used in the second etching process, and CF ₄ and H ₂ are used in the second etching process. In addition, No.4-6 uses the ArF photoresist of methacrylic resin as the photoresist layer 153, and the third etching process of each uses linear C ₅ F ₈ and O ₂ and Ar, wherein, No. 4 Use CF ₄ in the first etching process, do not perform the second etching process, No. 5 use CF ₄ in the first etching process, use CF ₄ and H ₂ in the second etching process, No. 6 in the first etching process H ₂ is used in the etching process, and CF ₄ and H ₂ are used in the second etching process.

After all the steps were completed, the shape deformation of the photoresist layer 153 was investigated for the samples under each condition. As a result, among Nos. 1-3 using acrylic resin as the photoresist layer 153, No. 1 which did not perform the second etching process had longitudinal ribs as an index of deformation of the photoresist layer, while the second etching process was performed. No. 2 and No. 3 of No. 2 and No. 3 had no longitudinal ribs regardless of the gas used in the first etching step. On the other hand, among Nos. 4-6 using methacrylic resin having lower plasma resistance than acrylic resin as the ArF resist layer 153, No. 4 in which the second etching step was not performed had longitudinal ribs. In addition, in No. 5 in which CF ₄ was used in the first etching process and the second etching process was performed, there were few vertical lines, and it was confirmed that vertical lines were suppressed by the second etching process. No. 6 in which the second etching step was performed and the gas used in the first etching step was H ₂ did not have longitudinal ribs. That is, it was confirmed that when the photoresist layer 153 is made of a material with low resistance to plasma, in addition to the second etching step, by etching the antireflection layer ₁₅₂ with H in the first etching step, no Longitudinal ribs as an index of deformation of the photoresist layer.

Table 2 No. 1 2 3 4 5 6 ArF photoresist Acrylic Methacrylic resin first etching process Pressure (Pa) (value in brackets is mTorr) 6.7(50) 2.0(15) 6.7(50) 2.0(15) Power from the first high-frequency power supply (W) 1000 2200 1000 2200 Power from the second high frequency power supply (W) 100 100 100 100 Gas and Flow (mL/min) CF ₄ : 100 H ₂ : 100 CF ₄ : 100 H ₂ : 100 second etching process Pressure (Pa) (value in brackets is mTorr) none 2.7(20) none 2.7(20) Power from the first high-frequency power supply (W) 1800 1800 Power from the second high frequency power supply (W) 1800 1800 Gas and Flow (mL/min) CF ₄ : 120H ₂ : 180 CF ₄ : 120H ₂ : 180 third etching process Pressure (Pa) (value in brackets is mTorr) 6.7(50) 2.7(20) Power from the first high-frequency power supply (W) ¹ 800 ¹ 800 Power from the second high frequency power supply (W) 1150 1800 Gas and Flow (mL/min) C ₄ F ₆ : 25O ₂ : 26Ar : 700 Straight chain C ₅ F ₈ : 27O ₂ : 30Ar: 500 Longitudinal tendons have none none have few none

(Embodiment 5)

Here, with the plasma processing apparatus 1 shown in FIG. 1, the following steps are implemented: through the opening pattern 163a of the photoresist layer 163, the organic anti-reflection layer 162 is plasma-etched to the object W to be processed. The object to be processed is shown in FIG. 7A As shown, there is an etching target layer 161 (thickness example: 1500 nm) such as an SiO layer formed on a bottom layer ₁₆₀ such as Si, an organic anti-reflection layer 162 (thickness example: 60 nm) covering this etching target layer 161, and light Resist layer 163, this photoresist layer covers this organic anti-reflection layer 162, forms opening pattern 163a (diameter example: 0.18 micron), is made of ArF photoresist or F2 photoresist; And then, plasma etching etching object Layer 161, forming an opening pattern 161a.

Next, description will be made with reference to FIGS. 7A-7C and the flowchart of FIG. 8 .

As the ArF resist or F2 resist constituting the photoresist layer 163, alicyclic-containing acrylic resin, cycloolefin resin, cycloolefin-anhydrous maleic acid resin, methacrylic resin, or the like can be used.

As the organic antireflection layer 162, an organic polymer material can be used.

In addition, in the present embodiment, at least the surface of the upper electrode plate 24 of the plasma processing apparatus 1 is made of a material containing Si, such as single crystal Si and SiC.

First, the gate valve 32 is opened, and the object W is loaded into the processing container 2 (STEP 1 ), and placed on the electrostatic chuck 11 . Next, the gate valve 32 is closed, and after the pressure in the processing container 2 is decompressed by the exhaust device 35, the valve 28 is opened to supply H gas from the processing gas supply source ₃₀ (STEP2), and the pressure in the processing container 2 is reduced. for the specified value.

In this state, high-frequency power is provided from the first high-frequency power supply 40 and the second high-frequency power supply 50, and H _gas is plasmatized, and the organic anti-reflection layer 162 is etched through the opening pattern of the photoresist layer 163 (STPE3) (FIG. 7A). On the other hand, before and after the timing of supplying high-frequency power from the first high-frequency power source 40 and the second high-frequency power source 50, a DC voltage is applied to the electrodes 12 in the electrostatic chuck 11, so that the object W to be processed is electrostatically attracted to the electrostatic chuck 11. superior. After etching for a predetermined time, the supply of high-frequency power and etching gas is stopped, and the etching of the organic anti-reflection layer 162 is completed (FIG. 7B). The luminous intensity of a specific substance in the plasma is detected by an end point detector (not shown), and the etching process is ended accordingly.

In the case of this embodiment, in the process of etching the organic anti-reflection layer 162 with H _plasma , Si and _H plasma supplied from the upper electrode plate 24 made of Si at least on the surface act on the photoresist. layer 163, so that on the surface of the photoresist layer 163, a thin protective layer 163b made of Si—O or Si—C or the like is formed.

That is, it is considered that during the process of etching the organic anti-reflection layer 162 with _H2 plasma, a reaction with C or H on the surface of the photoresist layer 163 occurs, and as a result, a large amount of highly reactive C or O exists in the Depending on the state of the surface of the photoresist layer 163, these highly reactive C or O react with Si supplied from the upper electrode plate 24 to form a thin protective layer 163b containing a substance such as Si—C or Si—O.

In this way, when the organic anti-reflection layer 162 is plasma-etched through the opening pattern 163a of the photoresist layer 163, a thin protective layer 163b is formed on the surface of the photoresist layer 163, without other redundant processes, and the photolithography can be made The plasma resistance of the adhesive layer 163 is improved. Therefore, when the organic anti-reflection layer 162 is etched, surface roughness or streaks are not caused, and the plasma resistance of the photoresist layer 163 can be maintained high.

Next, provide for example C ₅ F ₈ and O ₂ and Ar (STEP4) in the same processing container or in other processing containers, as etching gas, according to the same step as etching the organic anti-reflection layer 162, through the photoresist layer 163 The opening pattern 163a is plasma-etched to etch the etching object layer 161 (STEP5). As a result, for example, an opening pattern 161 a with a high aspect ratio is formed in the etching target layer 161 ( FIG. 7C ). Thereafter, after the etching target layer 161 is etched, the object W to be processed is taken out of the processing container 2 through the gate valve 32 (STEP 6 ).

When etching the etching target layer 161, in the case of this embodiment, the protective layer 163b is formed on the surface of the photoresist layer 163, thereby becoming a high plasma-resistant state, so even when the etching target layer 161 is etched by plasma In this case, the plasma resistance of the photoresist layer 163 or the selectivity ratio of the etching target layer 161 to the photoresist layer 163 can also be kept high. Therefore, the surface roughness of the photoresist layer 163 and the inclusion of longitudinal ribs do not occur, and the etching target layer 161 can be plasma-etched at a high etching rate. As a result, the productivity of the plasma etching process is improved while eliminating other redundant processes. In addition, since vertical ribs are not generated in the opening pattern 163 a of the photoresist layer 163 , the precision of the opening pattern 161 a formed on the etching target layer 161 using the photoresist layer 163 as a mask is also improved.

In STEP 2 described above, He and N ₂ may be used instead of H ₂ from the viewpoint of improving the plasma resistance of the photoresist layer 163 . However, when He and N ₂ are used, the organic antireflection layer 162 is substantially not etched. In addition, even if there is no organic anti-reflection layer 162 , at this time, the treatment for improving the plasma resistance of the photoresist layer 163 can be exclusively performed by plasma treatment of at least one of H ₂ , He, and N ₂ .

Next, a modified example of the present embodiment will be described with reference to FIGS. 9A-9C and the flowchart of FIG. 10 .

In this modified example, an example is shown in which, after etching the organic anti-reflection layer 162 with plasma of CF ₄ gas, before etching the etching target layer 161, the photoresist layer is etched by plasma treatment with H ₂ gas. 163 is formed with a protective layer 163b.

That is, first, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 (STEP 11 ), and placed on the electrostatic chuck 11 . Then, the gate valve 32 is closed, and after the pressure in the processing container 2 is decompressed by the exhaust device 35, the valve 28 is opened, and CF gas is supplied from the processing gas supply source ₃₀ (STEP12), and the pressure in the processing container 2 is changed to for the specified value.

In this state, high-frequency power is provided from the first high-frequency power supply 40 and the second high-frequency power supply ₅₀ , and the CF gas is plasmatized, and the organic anti-reflection layer 162 is etched through the opening pattern of the photoresist layer 163 (STPE13) (FIG. 9A).

On the other hand, before and after the timing of supplying high-frequency power from the first high-frequency power source 40 and the second high-frequency power source 50, a DC voltage is applied to the electrodes 12 in the electrostatic chuck 11, so that the object W to be processed is electrostatically attracted to the electrostatic chuck 11. superior. After etching for a predetermined time, the supply of high-frequency power and etching gas is stopped, and the etching of the organic anti-reflection layer 162 is completed. The luminous intensity of a specific substance in the plasma is detected by an end point detector (not shown), and the etching process is ended accordingly.

Next, the gas supplied to the processing container 2 is switched to H ₂ gas (STEP 14), the H ₂ gas is plasmatized, and the H ₂ plasma and Si supplied from the upper electrode plate 24 are applied to the surface of the photoresist layer 163. A thin protective layer 163b made of Si—O, Si—C, etc. is formed on the surface of the photoresist layer 163 after a predetermined period of time (STEP 15) (FIG. 9B).

That is, in the case of this modified example, it is considered that during the plasma treatment of the photoresist layer 163, it reacts with C or H on the surface of the photoresist layer 163, and as a result, becomes highly reactive C or O. In a state where a large amount exists on the surface of the photoresist layer 163, highly reactive C or O reacts with Si supplied from the upper electrode plate 24 to become Si—C or Si—O, forming a thin protective layer 163b. The plasma resistance of the photoresist layer 163 is improved by the thin protective layer 163 b containing Si—O, Si—C, or the like.

Next, provide for example C ₅ F ₈ and Ar and O ₂ (STEP 16) in the same processing container or in other processing containers, as etching gas, according to the same step as etching the organic anti-reflection layer 162, through the photoresist layer 163 The opening pattern 163a is plasma-etched to etch the etching target layer 161 (STEP 17). Thus, for example, an opening pattern 161a of high aspect ratio is formed (FIG. 9C). Thereafter, after the etching target layer 161 is etched, the object W to be processed is taken out of the processing container 2 through the gate valve 32 (STEP 18 ).

When etching the opening pattern 161a of the etching target layer 161, in the case of this modified example, as described above, the protective layer 163b is formed on the surface of the photoresist layer 163, thereby becoming a state with high plasma resistance, so The plasma resistance of the photoresist layer 163 or the selectivity ratio of etching to the mask can be maintained high. Furthermore, the opening pattern 161 a can be formed by plasma etching at a high etching rate without causing surface roughness or mixing of longitudinal ribs in the photoresist layer 163 . As a result, the productivity of the plasma etching process is improved while eliminating other redundant processes.

In the formation process of the protective layer 163b in STEP 15 described above, He and N ₂ may be used instead of H ₂ along with H ₂ .

In addition, in this embodiment, the etching target layer 161 is not limited to Si oxide represented by SiO ₂ as an example, and other Si compounds such as Si nitride and Si carbide, single crystal Si, polycrystalline Si, organic materials, etc. can be applied. , organic-inorganic hybrid materials, metals, metal compounds, etc. In addition, in this embodiment mode, a resist material with low plasma resistance such as ArF resist or F2 resist is particularly effective, but not limited thereto, and even EB resists that are lithographically printed by electron beams are effective. The same effect can also be obtained with other organic photoresist layers such as UV resist, EUV resist, KrF resist, etc. Moreover, it is not limited to the photoresist layer, and may be other mask layers. Moreover, the structure of the plasma processing apparatus is not limited to that shown in FIG. 1 .

In addition, the upper electrode plate is used as the Si source when forming the protective layer, but it is not limited to this, and the components in the processing container, such as the focus ring, the seal ring, and the inner container, can also be used as the same Si source by including Si at least on the surface. source. Among them, since the upper electrode plate is provided with respect to the object to be processed, there is an advantage that the treatment for improving the plasma resistance can be uniformly performed within the surface of the object to be processed.

Next, examples based on this embodiment will be described.

The frequencies of the first high-frequency power supply 40 and the second high-frequency power supply 50 in each of the following examples and comparative examples were set to 60 MHz and 13.56 MHz, respectively.

(1) [Plasma treatment of photoresist layer]

Here, for the photoresist layer with the opening pattern formed covering the etching target layer, the plasma treatment of H ₂ , N ₂ , and He was carried out in Examples 1-3, and the photoresist layer was plasma-treated. Comparative example 1 in which plasma treatment was performed after bulking Ar. Perform plasma treatment for 1 min. ArF photoresist was used as the photoresist layer.

(Example 5-1)

Process container pressure: 2.01Pa (15mTorr)

High-frequency power from the first high-frequency power supply: 2200W

High-frequency power from the second high-frequency power supply: 100W

Processing gas and its flow rate: H ₂ , 0.1L/min(100sccm)

(Example 5-2)

Process container pressure: 2.01Pa (15mTorr)

High-frequency power from the first high-frequency power supply: 2200W

High-frequency power from the second high-frequency power supply: 100W

Processing gas and its flow rate: N ₂ , 0.1L/min(100sccm)

(Example 5-3)

Process container pressure: 2.01Pa (15mTorr)

High-frequency power from the first high-frequency power supply: 2200W

High-frequency power from the second high-frequency power supply: 100W

Processing gas and its flow rate: He, 0.1L/min (100sccm)

(Comparative Example 5-1)

Process container pressure: 2.01Pa (15mTorr)

High-frequency power from the first high-frequency power supply: 2200W

High-frequency power from the second high-frequency power supply: 100W

Processing gas and its flow rate: Ar, 0.1L/min (100sccm)

Fig. 11A and Fig. 11B represent the surface analysis results after plasma treatment in the photoresist layer after using acrylic and methacrylic ArF photoresists respectively (represented by H ₂ , N ₂ , He, Ar line graph). As shown in the figure, in Examples 5-1 to 5-3, for any ArF photoresist of acrylic and methacrylic, it can be observed that the respective plasmas based on H ₂ , N ₂ , and He can In the plasma treatment of the bulk, a protective layer containing a substance having bonding energy equivalent to Si—O or Si—C exists on the surface of the photoresist layer.

In contrast, in the case of the Ar-based plasma treatment of Comparative Example 5-1, for either acrylic and methacrylic ArF resists, only adhesion of Si supplied from the upper electrode plate was observed.

The plasma resistance is improved by adhering Si to the surface of the photoresist layer, but in this case, after ashing, a defect occurs in which Si is adhering to the vicinity of the hole of the etching target layer. From this point of view, it was confirmed that H ₂ , N ₂ , and He are preferably used in the plasma treatment.

(2) [Plasma treatment of photoresist layer after etching organic anti-reflection layer]

For the object W to be processed having an etching target layer, an organic anti-reflection layer covering the etching target layer, and a photoresist layer covering the organic anti-reflection layer and forming an opening pattern, the organic anti-reflection layer is etched under the following conditions, and then, The photoresist layer 163 was plasma-treated under the same conditions as in Examples 5-1 to 5-3 and Comparative Example 5-1 (FIG. 9A, 9B, STEP 11-15 in FIG. 10).

Process container pressure: 6.7Pa (50mTorr)

High-frequency power from the first high-frequency power supply: 1000W

High-frequency power from the second high-frequency power supply: 100W

Processing gas and its flow rate: CF ₄ , 0.1L/min(100sccm)

Next, the etching target layer 161 is etched under the following conditions (FIG. 9C, STEP 16-18 in FIG. 5).

Process container pressure: 2.01Pa (15mTorr)

High-frequency power from the first high-frequency power supply: 2170W

High-frequency power from the second high-frequency power supply: 1550W

Etching gas and its flow rate:

cC ₅ F ₈ : 0.015L/min(15sccm)

Ar: 0.380L/min (380sccm)

O ₂ : 0.019L/min(19sccm)

As described above, after performing etching of the etching target layer, the cross-sectional shape of the etched portion of each object to be processed was observed by photographing with an electron microscope. As a result, in the object to be treated after the photoresist layer made of ArF photoresist was treated with H ₂ , N ₂ , He, and Ar plasma, the surface roughness of the photoresist layer or the incorporation of vertical ribs. On the contrary, in the object to be processed in which the photoresist layer was not subjected to the plasma treatment in the above-mentioned steps, the surface of the photoresist was rough or mixed with vertical lines.

In addition, when the plasma treatment of the photoresist layer is performed after etching the organic antireflection layer and before etching the etching target layer, it is different from performing the plasma treatment of the photoresist layer 163 before etching the organic antireflection layer and the etching target layer. Compared with the case of bulk processing, the surface of the ArF photoresist layer after etching the etching target layer has a rough surface or less longitudinal ribs. Therefore, in etching the organic anti-reflection layer, _CF4 plasma, which has a high etching rate and less damage to the ArF photoresist, is used, and then the plasma treatment of the ArF photoresist layer is performed. Etching can improve productivity and etching accuracy.

(Embodiment 6)

Here, using the plasma processing apparatus 1 of FIG. 1 , the process of plasma etching the anti-reflection layer 172 through the opening pattern 173a of the photoresist layer 173 is performed on the object W in FIG. The bottom layer 171 made of _SiO , the anti-reflection layer 172 covering the bottom layer 171, and the photoresist layer 173, the photoresist layer covers the anti-reflection layer 172, is formed with an opening pattern, and is made of ArF photoresist or F2 photoresist. The engraving composition. In this embodiment mode, as the ArF resist and the F2 resist, acrylic resin containing alicyclic, cycloolefin resin, cycloolefin-anhydrous maleic acid resin, etc. can be used. In addition, as the antireflection layer 62, either an inorganic type or an organic type may be used, for example, amorphous carbon or an organic polymer material which is a carbonaceous material may be used.

For etching, first, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Next, close the gate valve 32, depressurize the inside of the processing container 2 through the exhaust device 35, open the valve 28, supply the above-mentioned processing gas, such as C ₂ F ₄ and O ₂ , from the processing gas supply source 30, and process The pressure in the container 2 becomes a predetermined value.

In this state, high-frequency power is applied to the upper electrode 21 and the susceptor 5 serving as the lower electrode to plasmatize the processing gas, and the antireflection layer 172 in the object W to be processed is etched through the opening pattern 173a of the photoresist layer 173. . On the other hand, before and after the timing of applying high-frequency power to the upper and lower electrodes, a DC voltage is applied to the electrodes 12 in the electrostatic chuck 11 to electrostatically attract the object W to the electrostatic chuck 11 .

During etching, an end point detector (not shown) detects a predetermined luminescence intensity, and the etching is terminated based on this.

In this embodiment, the antireflection layer 172 is etched through the photoresist layer 173 by using a processing gas containing C ₂ F ₄ , for example, a processing gas containing C ₂ F ₄ and O ₂ , thereby inhibiting the photoresist layer 173 The rough surface maintains a high selectivity ratio of the anti-reflection layer to the photoresist layer, and at the same time, increases the etching rate of the anti-reflection layer 172 .

In addition, in this embodiment, this invention is not limited to the said embodiment, Various deformation|transformation is possible. For example, the case where the antireflection layer is used as the layer to be etched is shown, but it is not limited thereto, and other layers may be etched. In addition, the processing gas containing C ₂ F ₄ is not limited to containing C ₂ F ₄ and O ₂ . Also, in the case of using a process gas containing C ₂ F ₄ and O ₂ , the mask layer is not limited to ArF photoresist or F2 photoresist, and other photoresists can also be used, and non- photoresist layer. In addition, the structure of the etching device is not limited to that shown in FIG. 1 .

Next, examples based on this embodiment will be described.

First, the conditions of the examples are as follows. That is, the pressure inside the processing container is set to 1.33Pa (10mTorr) and _6.66Pa (50mTorr), and the flow ratio of _C2F4 to _O2 in the processing gas is set to _{C2F4 : O2} =5:2,3 : 2, 5: 4, 1: 1, 3: 4, apply 600, 1000, 1400 W high-frequency power with a frequency of 60 MHz to the upper electrode, and apply 100 W with a frequency of 2 MHz to the lower electrode.

On the other hand, the conditions of the comparative example are as follows. That is, the pressure inside the processing container is set to 6.66Pa (50mTorr), the processing gas is set to _CF4 , high-frequency power with a frequency of 60MHz is applied to the upper electrode at 1000W, and high-frequency power at a frequency of 2MHz is applied to the lower electrode at 100W .

After etching was performed under this condition, the selectivity ratio of the antireflection layer to the ArF resist layer (etching rate of the antireflection layer/etching rate of the ArF resist layer) did not change much in Examples and Comparative Examples, but The etching rate of the anti-reflection layer in Examples is 1.2-3.6 times that in Comparative Examples. In addition, the surface roughness of the ArF resist layer did not occur in both the comparative example and the working example. From this, it was confirmed that in the examples, the antireflection film can be etched at a high etching rate without causing the surface roughness of the ArF resist layer.

(Embodiment 7)

Here, the process of etching the anti-reflection layer 182 through the opening pattern 183a of the photoresist layer 183 with respect to the object W of FIG. 13A using the plasma processing apparatus 1 of FIG. ₁ described above; layer 181, the object W to be processed has a _SiO2 layer 181 as an etching target, an anti-reflection layer 182 covering the layer 181, and a photoresist layer 183. The photoresist layer covers the anti-reflection layer 182, and the ArF photoresist or F2 photoresist. In this embodiment mode, as ArF resist and F2 resist, acrylic resin containing alicyclic, cycloolefin resin, cycloolefin-anhydrous maleic acid resin can be used. As the antireflection layer, an organic polymer material or amorphous carbon can be used.

First, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Next, the gate valve 32 is closed, and after the inside of the processing container 2 is decompressed by the exhaust device 35, the valve 28 is opened, and an etching gas containing a substance containing C and F and a substance containing H is supplied from the processing gas supply source 30, And the pressure in the processing container 2 is changed to a predetermined value, for example, 6.66 Pa (50 mTorr). In this state, high-frequency power is applied to the upper electrode 21 and the susceptor 5 as the lower electrode to plasmatize the etching gas, and the antireflection layer 182 in the object W to be processed is etched ( FIG. 13A ). This increases the remaining film amount of the photoresist layer 183 after the antireflection layer 182 has been etched, and forms a hole or groove having a desired opening shape in the subsequent etching step of the etching target portion.

As a substance containing C and F used in this etching, CF ₄ which causes little damage to the ArF resist layer is exemplified. In addition, as substances having H, hydrocarbons, H2, and hydrofluorocarbons can be used. As hydrocarbons, CH ₄ and the like are exemplified. As the hydrofluorocarbon, a substance having a ratio of the atomic number of H to the atomic number of F is preferably 3 or more, and CH ₃ F is exemplified as such a substance. In the case of using CH ₃ F, by setting the ratio of the flow rate of CH ₃ F to the flow rate of substances containing C and F in the etching gas at 0.04-0.07, compared with the case where CH ₃ F is not added at all, the etching can be completed. The remaining film amount of the ArF photoresist layer after the antireflection layer increases.

On the other hand, before and after the timing of applying high-frequency power to the upper and lower electrodes, the DC power supply 13 is applied to the electrodes 12 in the electrostatic chuck 11 to electrostatically attract the object W to the electrostatic chuck 11 . In this way, after the etching of the anti-reflection layer 182 is completed, the supply of the etching gas and the high-frequency power is stopped.

Next, another etching gas, such as a mixed gas of C ₅ F ₈ , O _{2 ,} and Ar, is supplied into the processing container 2 to adjust the pressure in the processing container 2 to a predetermined value, such as 2.00 Pa (15 mTorr). A high-frequency power is applied to the upper electrode 21 and the lower susceptor 5 to plasmatize the etching gas to etch the SiO ₂ layer 181 in the object W to be processed ( FIG. 13B ). During etching, an end point detector (not shown) detects a predetermined luminescence intensity, and the etching is terminated based on this.

In addition, the etching target part is not limited to the above-mentioned SiO ₂ layer, and can also be applied to oxide films (oxygen compounds) such as TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic Si oxide film, CORAL (Noberas Corporation), etc. ) or etching of low-dielectric organic insulating films, etc. In addition, the structure of the applicable plasma processing apparatus is not limited to that shown in FIG. 1 .

Next, examples based on this embodiment will be described.

The processed body shown in FIG. 13A has a _SiO2 layer (a film thickness of 2 micrometers), an anti-reflection layer (a film thickness of 60 nm) covering this layer, and an ArF photoresist layer (a film thickness of 360 nm) covering this layer. ) object to be processed.

The etching conditions of the antireflection layer in the examples are as follows. That is, the pressure in the processing container 2 is set to 6.66Pa (50mTorr), and the etching gas is set to _CF4 (flow rate: 100mL/min (sccm)) and _CH3F (flow rate: 4 or 7mL/min (sccm)) 1000W of high-frequency power is applied to the upper electrode from a high-frequency power supply with a frequency of 60MHz, and a high-frequency power of 100W is applied to the bottom electrode from a high-frequency power supply with a frequency of 2MHz. Alternatively, H ₂ (at a flow rate of 5, 10 or 15 mL/min(sccm)), CH ₂ F ₂ (at a flow rate of 5 or 10 mL/min(sccm)) and CHF ₃ (at a flow rate of 10, 30, 50 or 70 mL /min(sccm)) instead of CH ₃ F etching gas is also etched.

In the comparative example, the etching gas was only CF ₄ (the flow rate was 100 mL/min (sccm)), and other etching conditions were the same as those in the examples.

The anti-reflection film 182 was etched under the conditions of the above examples and comparative examples, and the thickness of the remaining film of the ArF photoresist layer after a certain etching time was measured, and the following results were obtained.

In an example, when CH ₃ F is used, the flow rate is 375 nm at 4 mL/min, and 405 nm at 7 mL/min. In the case of using _H2 , it is 345nm when its flow rate is 5mL/min, and 360nm when it is 10mL/min and 15mL/min. In the case of using CH ₂ F ₂ , the flow rate is 345 nm at 5 mL/min, and 400 nm at 10 mL/min. When CHF ₃ is used, the flow rate is 350 nm at 10 mL/min, 360 nm at 30 mL/min, 360 nm at 50 mL/min, and 390 nm at 70 mL/min. In contrast, it was 330 nm in the comparative example.

From the above, it was confirmed that in any of the examples, the thickness of the remaining film was increased compared to the comparative example. This is considered to be because the F active species that etched the ArF resist layer reacted moderately with the H active species generated from the gas containing H to become a gas such as HF, which was discharged out of the processing container.

Additionally, _CH3F is preferred in these examples. It is considered that the remaining film amount is large despite the low flow rate of CH ₃ F because the number of H atoms in the molecule is greater than the number of F atoms. Among them, it is presumed that in chemically stable substances such as H ₂ , even if H active species are generated, there is an advantage in reacting with other H active species and then bonding after reacting with F active species, so the amount of remaining film is larger than other substances. .

Therefore, it is confirmed that it is preferable to destabilize the substance itself to some extent, and there are many H atoms in the substance, such as hydrocarbons (CH ₄ , C ₂ H _{4 ,} etc.), or hydrofluorocarbons (especially the number of H atoms The ratio of the number of atoms to F is 3 or more, for example, CH ₃ F), etc. are mixed into the etching gas. In addition, in the case of using CH ₃ F, it was confirmed that the remaining film amount can be increased even if the ratio of the flow rate of CH ₃ F to the flow rate of CF ₄ , which is a substance having C and F, is as low as 0.04-0.07.

(Embodiment 8)

Here, using the plasma processing apparatus 1 of FIG. 1 described above, the process of etching the anti-reflection layer 192 through the opening pattern 193a of the photoresist layer 193 is performed on the object W of FIG. _14A ; layer 191, the object W to be processed has a _SiO2 layer 191 as an etching target, an anti-reflection layer 192 covering this layer 191, and a photoresist layer 193 covering the anti-reflection layer 192, which is photolithography by ArF glue or F2 photoresist. In this embodiment mode, as ArF resist and F2 resist, acrylic resin containing alicyclic, cycloolefin resin, cycloolefin-anhydrous maleic acid resin can be used. As the antireflection layer, an organic polymer material or amorphous carbon can be used.

First, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Next, the gate valve 32 is closed, and after the inside of the processing container 2 is decompressed by the exhaust device 35, the valve 28 is opened, and the first etching gas containing a substance having C and F and CO, such as, for example, is supplied from the processing gas supply source 30 A mixed gas of CF ₄ and CO is used to change the pressure in the processing container 2 to a predetermined value, for example, 13.3 Pa (100 mTorr). In this state, high-frequency power is applied to the upper electrode 21 and the susceptor 5 as the lower electrode, and the first etching gas is plasmaized to etch the antireflection layer 192 in the object W to be processed ( FIG. 14A ). On the other hand, before and after the timing of applying high-frequency power to the upper and lower electrodes, the DC power supply 13 is applied to the electrodes 12 in the electrostatic chuck 11 to electrostatically attract the object W to the electrostatic chuck 11 . After the etching of the antireflection layer 192 is finished, the supply of the first etching gas and the high frequency power is stopped.

Next, a second etching gas, for example, a gas containing fluorocarbons such as C ₅ F ₈ and C ₄ F ₆ , specifically C ₅ F ₈ or C ₄ F ₆ , O ₂ and Ar, is supplied into the processing container 2. The mixed gas adjusts the pressure in the processing container 2 to a predetermined value for the second etching, for example, 2.00 Pa (15 mTorr). High-frequency power is applied to the upper electrode 21 and the lower susceptor 5 to plasmatize the second etching gas to etch the SiO ₂ layer 191 in the object W to be processed ( FIG. 14B ). During etching, an end point detector (not shown) detects a predetermined luminescence intensity, and the etching is terminated based on this.

In addition, the etching target part is not limited to the above-mentioned SiO ₂ layer, and can also be applied to oxide films (oxygen compounds) such as TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic Si oxide film, CORAL (Noberas Corporation), etc. ) or etching of low-dielectric organic insulating films, etc. In addition, the structure of the applicable plasma processing apparatus is not limited to that shown in FIG. 1 .

Next, examples based on this embodiment will be described.

The object to be processed shown in FIG. 14A is used as the object to be processed. The first etching conditions of the examples are as follows. That is, the pressure in the processing container 2 is set to 6.66Pa (50mTorr) or 13.3Pa (100mTorr), and the flow rate of the first etching gas is set to _CF4 : 75, 100, or 200mL/min (sccm), CO: 25, 100 or 200mL/min (sccm), apply 1000, 1500 or 2000W high-frequency power to the upper electrode from a 60MHz frequency high-frequency power supply, and apply 100W high-frequency power to the lower electrode from a 2MHz frequency high-frequency power supply.

The first etching conditions of the comparative example are as follows. That is, the pressure in the processing container 2 was set to 6.66Pa (50mTorr), and _only CF was added at a flow rate of 100mL/min (sccm) as the first etching gas (CO was not added), and the frequency and applied power of the high-frequency power supply were Same as Example.

The second etching conditions of Examples and Comparative Examples are as follows. That is, the pressure in the processing container 2 is set to 2.00 Pa (15 mTorr), and the flow rates of C ₅ F ₈ , O ₂ , and Ar of the second etching gas are set to 15, 19, and 380 mL/min (sccm), respectively, from 60 MHz to A high-frequency power supply with a frequency of 2170 W was applied to the upper electrode, and a high-frequency power supply with a frequency of 2 MHz was applied to the lower electrode with a high-frequency power of 1550 W.

As a result of performing the first etching and the second etching under the above conditions, the selectivity ratio of the _SiO2 layer to the ArF photoresist layer in the second etching process (etching rate of the _SiO2 layer/etching rate of the ArF photoresist layer) It is larger in Examples than in Comparative Examples. For example, the first etching condition of the embodiment is pressure: 13.3Pa (100mTorr), CF ₄ flow rate: 75mL/min (sccm), CO flow rate: 25mL/min (sccm), upper electrode applied power: 1000W when the above selection ratio It was 9.7, and the above selection ratio of the comparative example was 6.3.

In addition, in the second etching step, when C ₄ F ₆ is used instead of C ₅ F ₈ , the above selectivity is higher in the example (the first etching gas is CF ₄ and CO) than in the comparative example (the first etching gas High only for CF ₄ ).

Since it is considered that a protective film having interbonding between carbon elements is formed on the surface of the ArF photoresist layer by plasma containing a gas containing C and F and CO, only by irradiating the surface of the ArF photoresist layer containing a gas containing C and F The plasma of the substance of F and the gas of CO can improve the plasma resistance of the ArF photoresist layer.

In addition, the present invention can also be applied to a mask layer other than an ArF resist layer that does not have the effect of improving plasma resistance in the case of an ArF resist layer.

In addition, the second etching gas is not limited to a gas containing C ₅ F ₈ or C ₄ F ₆ , and a gas containing other fluorine-containing compounds such as fluorocarbons and hydrofluorocarbons may also be used.

(Embodiment 9)

Here, using the plasma processing apparatus 1 shown in FIG. 1 above, implement the following steps: plasma etch the organic anti-reflection layer 202 on the object W to be processed through the opening pattern of the photoresist layer 203. The object to be processed is shown in FIG. As shown, there are _SiO2 layer 201 as etching target, organic anti-reflection layer 202 covering this _SiO2 layer 201, and photoresist layer 203. The photoresist layer covers this organic anti-reflection layer 202, and an opening pattern 203a is formed. , composed of ArF photoresist or F2 photoresist; and then, the _SiO2 layer 201 is plasma etched. In this embodiment mode, as ArF resist or F2 resist, acrylic resin containing alicyclic, cycloolefin resin, cycloolefin-anhydrous maleic acid resin can be used. As the organic antireflection layer 202, for example, an organic polymer material can be used.

First, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Next, the gate valve 32 is closed, and after the pressure in the processing container 2 is decompressed by the exhaust device 35, the valve 28 is opened, and the etching gas containing SiF ₄ as a Si-containing material is supplied from the processing gas supply source 30, and the processing container is depressurized. 2 to the specified value. Other Si-containing substances may be used instead of SiF ₄ , but SiF ₄ is preferable from the viewpoint of increasing the etching rate of the organic antireflection layer 202 . In addition to Si-containing substances, the etching gas may also contain CHF ₃ , HBr, He or H ₂ , for example, SiF ₄ and H ₂ are used.

In this state, high-frequency power is supplied from the first and second high-frequency power sources 40 and 50 to plasmatize the etching gas and pass through the opening pattern 203 a of the photoresist layer 203 to etch the organic anti-reflection layer 202 . On the other hand, before and after the timing when high frequency power is supplied from the first and second high frequency power sources 40 and 50 , a DC voltage is applied to the electrodes 12 in the electrostatic chuck 11 to electrostatically attract the object W to the electrostatic chuck 11 . After etching for a predetermined time, the supply of high-frequency power and etching gas is stopped, and the etching of the organic anti-reflection layer 202 is completed. A predetermined luminous intensity is detected by an end point detector (not shown), and the etching process is terminated based on this.

Next, in the same processing chamber or in other processing chambers, the SiO ₂ layer 201 is plasma etched through the opening pattern 203 a of the photoresist layer in the same steps as the etching of the organic anti-reflection layer 202 . As the etching gas at this time, for example, C ₄ F ₆ , O ₂ , and Ar can be used, but not limited thereto.

In this way, when the organic anti-reflection film 202 is plasma-etched through the opening pattern of the photoresist layer 203, since SiF ₄ gas is used as a gas containing Si, a layer containing Si is formed on the surface of the photoresist layer 203 during etching. A thin cured layer can improve the plasma resistance of the photoresist layer 203 . Therefore, when etching the organic anti-reflective layer 202, surface roughness or mixing of longitudinal ribs will not occur, and the plasma resistance of the photoresist layer 203 made of ArF photoresist or F2 photoresist with low plasma resistance can be improved. Keep it high. At this time, when the etching gas of the organic anti-reflection layer 202 contains H ₂ , since the C=O bond on the surface of the photoresist layer 203 is converted into a chemically strong CC bond or C=C bond, in the above-mentioned photolithography Forming a thin cured layer containing Si on the surface of the adhesive layer 203 can further improve plasma resistance.

In addition, after etching the organic antireflection layer 202 in this way, the _SiO2 layer 201, which is the layer to be etched, is etched through the opening pattern 203a of the photoresist layer 203, so the plasma resistance is improved when the organic antireflection layer 202 is etched. The photoresist layer 203 can maintain high plasma resistance even when the SiO ₂ layer 201 to be etched is plasma-etched, and the photoresist layer can be plasma-etched without roughening the surface or mixing vertical lines.

In addition, the etching target layer is not limited to Si oxide represented by SiO ₂ , and other Si compounds such as Si nitride and Si carbide, single crystal Si, polycrystalline Si, organic materials, organic-inorganic hybrid materials, metals, etc. , metal compounds, etc. In addition, the structure of the plasma processing apparatus is not limited to that shown in FIG. 1 .

Next, examples based on this embodiment will be described.

Here, using the object to be processed having the structure of FIG. 15 , etching of organic antireflection layers with Si-containing substances using various etching gases (Examples 9-1 to 9-7) and without Si-containing substances were performed. Etching of the organic anti-reflection layer using an etching gas (Comparative Examples 9-1, 9-2).

The frequencies of the first and second high-frequency power supplies in the respective examples and comparative examples were set to 60 MHz and 13.56 MHz, respectively. In addition, after etching the organic antireflection layer in each of Examples and Comparative Examples under the following conditions, the SiO ₂ layer was plasma-etched under the etching conditions described later.

Etched organic anti-reflection layer

(Example 9-1)

Process container pressure: 0.67Pa (5mTorr)

High-frequency power from the first high-frequency power supply: 300W

High-frequency power from the second high-frequency power supply: 60W

Etching gas and its flow rate: SiF ₄ , 0.08L/min (80sccm)

(Example 9-2)

Process container pressure: 6.7Pa (50mTorr)

High-frequency power from the first high-frequency power supply: 700W

High-frequency power from the second high-frequency power supply: 100W

Etching gas and its flow rate: SiF ₄ , 0.1L/min(100sccm)

(Example 9-3)

Process container pressure: 0.67Pa (5mTorr)

High-frequency power from the first high-frequency power supply: 300W

High-frequency power from the second high-frequency power supply: 60W

Etching gas and its flow rate: SiF ₄ , 0.04L/min (40sccm)

CHF ₃ , 0.04L/min(40sccm)

(Example 9-4)

Process container pressure: 0.67Pa (5mTorr)

High-frequency power from the first high-frequency power supply: 300W

High-frequency power from the second high-frequency power supply: 60W

Etching gas and its flow rate: SiF ₄ , 0.04L/min (40sccm)

HBr, 0.04L/min(40sccm)

(Example 9-5)

Process container pressure: 0.67Pa (5mTorr)

High-frequency power from the first high-frequency power supply: 300W

High-frequency power from the second high-frequency power supply: 60W

Etching gas and its flow rate: SiF ₄ , 0.04L/min (40sccm)

He, 0.04L/min(40sccm)

(Example 9-6)

Process container pressure: 0.67Pa (5mTorr)

High-frequency power from the first high-frequency power supply: 300W

High-frequency power from the second high-frequency power supply: 60W

Etching gas and its flow rate: SiF ₄ , 0.04L/min (40sccm)

HBr, 0.02L/min(20sccm)

He, 0.02L/min(20sccm)

(Example 9-7)

Process container pressure: 6.7Pa (50mTorr)

High-frequency power from the first high-frequency power supply: 1000W

High-frequency power from the second high-frequency power supply: 100W

Etching gas and its flow rate: SiF ₄ , 0.03L/min(30sccm)

H ₂ , 0.02L/min(20sccm)

(Comparative Example 9-1)

Process container pressure: 0.93Pa (7mTorr)

High-frequency power from the first high-frequency power supply: 100W

High-frequency power from the second high-frequency power supply: 250W

Etching gas and its flow rate: CF ₄ , 0.072L/min (72sccm)

CHF ₃ , 0.026L/min(26sccm)

O ₂ , 0.006L/min(6sccm)

(Comparative Example 9-2)

Process container pressure: 6.7Pa (50mTorr)

High-frequency power from the first high-frequency power supply: 1000W

High-frequency power from the second high-frequency power supply: 100W

Etching gas and its flow rate: CF ₄ , 0.1L/min (100sccm)

Etched _SiO2 layer

(Example 9-1, 9-3 to 9-6 and Comparative Example 9-1)

Process container pressure: 16Pa (120mTorr)

High-frequency power from the first high-frequency power supply: 550W

High-frequency power from the second high-frequency power supply: 350W

Etching gas and its flow rate: CF ₄ , 0.1L/min (100sccm)

CHF ₃ , 0.06L/min(60sccm)

(Example 9-2, 9-7 and Comparative Example 9-2)

Process container pressure: 2.7Pa (20mTorr)

High-frequency power from the first high-frequency power supply: 1800W

High-frequency power from the second high-frequency power supply: 1150W

Etching gas and its flow rate: C ₄ F ₆ , 0.025L/min(25sccm)

O ₂ , 0.026L/min(26sccm)

Ar, 0.7L/min (700sccm)

As described above, after the etching of the SiO ₂ layer 201 was performed, the cross-sectional shape of the etched part of the object W in each of the Examples and Comparative Examples was observed by photographing with an electron microscope. As a result, in 9-1 to 9-7, the surface roughness of the ArF photoresist layer 203 or the incorporation of longitudinal ribs were basically not seen, but in Comparative Examples 91- and 9-2, ArF photoresist The surface of layer 203 is rough or mixed with longitudinal ribs.

(Embodiment 10)

Here, using the plasma processing apparatus shown in FIG. 1, the following series of steps are performed on an object W having an etching target layer composed of Si oxide represented by a _SiO2 film as shown in FIG. 16A. 211, and a mask layer 212 made of ArF photoresist or F2 photoresist covering the etching target layer 211. In the present embodiment, as the ArF resist or the F2 resist, an acrylic resin containing an alicyclic group, a cycloolefin resin, a cycloolefin-anhydrous maleic acid resin, a methacrylic resin, or the like can be used. Also in this embodiment, the upper electrode plate 24 of the shower head in the apparatus of FIG. 1 is made of Si.

First, the gate valve 32 is opened, and the object W to be processed is carried into the processing container 2 and placed on the electrostatic chuck 11 . Next, close the gate valve 32, after depressurizing in the processing container 2 by the exhaust device 35, open the valve 28, provide an inert gas, such as Ar, from the processing gas supply source 30, and change the pressure in the processing container 2 to For example 1.33Pa (10mTorr). As the inert gas, other gases such as Kr and Xe can also be used. In this state, high-frequency power is applied from high-frequency power sources 40 and 50 to the upper electrode and the susceptor 5 as the lower electrode, at least a part of the inert gas is plasmatized, and the upper electrode plate 24 made of Si is sputtered. On the other hand, before and after the timing of applying high-frequency power to the upper and lower electrodes, the DC power supply 13 is applied to the electrodes 12 in the electrostatic chuck 11 to electrostatically attract the object W to the electrostatic chuck 11 .

At this time, the high-frequency power applied to the upper electrode 21 is energy for ionizing the inert gas. By sputtering the upper electrode plate 24 made of Si in this way, a Si-containing layer 213 is formed on the surface of the mask layer 212 as shown in FIG. 16B . The shorter the time for forming the Si-containing layer 213 on the surface of the mask layer 212, the less the effect of improving the plasma resistance, and the longer it is, the longer the Si-containing layer 213 is formed on the surface of the etching target layer 211 in the opening part of the mask layer 212. A large amount of Si-containing layers hinders subsequent etching, so it is preferable to select an appropriate time. For example, the frequency of high-frequency power applied to the upper electrode 21: 60 MHz, power: 2000 W, the frequency of high-frequency power applied to the susceptor 5: 2 MHz, and power: 100 W can be used, but under these conditions, the above-mentioned Processing times were in the range of 60-90 seconds.

In addition, in terms of power, compared with the case where the power applied to the upper electrode is 1250W and the power applied to the susceptor is 400W (the so-called Vpp is lowered), the above conditions can reduce the opening of the mask layer when forming the Si-containing layer. change in shape. If Vpp is too high, the opening of the mask layer will be enlarged, making it impossible to form a hole or a trench having an opening pattern designed in a subsequent etching step.

After the formation of the Si-containing layer on the surface of the mask layer was completed, the application of high-frequency power was stopped.

Thereafter, an etching gas is introduced into the processing chamber 2, high-frequency power is applied to the upper electrode 21 and the susceptor 5, and the etching target layer 211 is etched. For example, when the etching target layer 211 is formed of Si oxide, it is preferably a gas containing at least one selected from C ₄ F ₆ , C ₄ F ₈ , and C ₅ F ₈ . As this etching gas, a mixed gas of C ₄ F ₆ , O ₂ and Ar is exemplified. In addition, the pressure in the processing container 2 is 2.67 Pa (20 mTorr), and the high-frequency power applied to the upper electrode 21 and the susceptor 5 are 1600 W and 800 W, respectively. The frequency of the high-frequency power at this time is the same as that at the time of sputtering, and examples are 60 MHz and 2 MHz. By applying high-frequency power, the etching gas is plasmatized, and the etching target layer 211 made of, for example, Si oxide is etched. After the etching is finished, the application of etching gas and high-frequency power is stopped.

Under the conditions of the above example, after etching the etching target layer 211 made of Si oxide, the selectivity ratio of the etching target layer 211 to the mask layer 212 (etching rate of the etching target layer/etching rate of the mask layer) was 28.8 . In the case where etching is not performed to form the Si-containing layer on the surface of the mask layer 212, the above-mentioned selectivity ratio is 8.2.

After etching in this way, a step of removing the mask layer 212 on which the Si-containing layer 213 is formed on the surface (ashing step) is performed next. Here, an example is shown when the removal of the mask layer 212 on which the Si-containing layer 213 is formed on the surface is performed in multiple stages.

In the first stage, a fluorine-containing gas, such as CF ₄ , is introduced into the processing container 2, and high-frequency power is applied to the upper electrode and the susceptor 5 for a predetermined time, so that the Si-containing gas formed on the mask layer 212 is basically completely removed. Layer 213. This is because if the Si-containing layer remains, the Si-containing substance will adhere to the surface of the object to be processed when the removal of the mask layer 212 is completed in the next second stage. At this time, the pressure in the example processing container 2 is 6.66Pa (50mTorr), the high-frequency power applied to the upper electrode 21 and the susceptor 5 is 1600W and 800W respectively, and the frequencies are the same as those in sputtering, 60MHz and 2MHz. Under this condition, the Si-containing layer 213 can be substantially completely removed by processing for 90 seconds.

In addition, as the gas at this time, when using a gas in which O ₂ and Ar are added to CF ₄ , it will damage the mask layer 212 made of ArF resist. Therefore, it is preferable to use only CF ₄ gas, or add a small amount in the case of adding O ₂ and Ar etc. to CF ₄ .

Gases other than CF ₄ may be used as the fluorine-containing compound gas, but CF ₄ is preferably used from the viewpoint of reducing damage to the mask layer 212 made of ArF resist or the like at the bottom of the Si-containing layer 213 .

In the second stage, a predetermined processing gas is introduced, high-frequency power is applied to the upper electrodes 21 and the base 5 as the lower electrodes, and the mask layer 212 itself after most of the Si-containing layer 213 has been removed is removed. At this time, as the processing gas, it is preferable to use a gas not containing a fluorine compound, for example, only _O2 gas, or a mixed gas containing _O2 and _N2 or Ar, or a mixed gas of O2 _{, N2} and _H2 , or the like.

This second stage of processing is actually performed. At this time, pressure, high-frequency power, frequency of high-frequency power supply, etc. are not changed from the first stage, and only the process gas is changed to perform ashing. O ₂ is used here. When the object to be processed from which the mask layer 212 has been removed is observed, the opening shape and cross-sectional shape of the holes or grooves are substantially the same as designed. In addition, Si-containing substances do not adhere to the object to be processed.

In the present embodiment, as described above, the inert gas is ionized by the energy when high-frequency power is applied to the parallel plate-shaped electrode, thereby sputtering the upper electrode plate 24 made of Si and adhering to the mask layer 212. , Forming a Si-containing layer, so compared with the mask layer itself, the plasma resistance can be greatly improved. Especially in the case of using ArF resist or F2 resist with low plasma resistance as the mask layer 212, the effect of improving the plasma resistance is remarkable.

In addition, in the ashing after etching the etching target layer, the Si-containing layer 213 and the mask layer 212 itself are removed in multiple stages, so even when the Si-containing layer 213 and the mask layer are formed, it is possible to perform Layer property removal. Needless to say, the Si-containing layer 213 and the mask layer 212 may also be removed at one time. Compare the combined advantages and disadvantages of multi-stage removal versus one-shot removal to determine which to use.

In addition, as the target when the Si-containing layer is formed in the mask layer by sputtering, it is not limited to the upper electrode plate of the above-mentioned example, if it is arranged in the processing container, and at least a part of the surface is a member of Si, then it may be a focusing target. Other components such as rings, or configure Si components as targets. In addition, another Si wafer itself (bare wafer) which has not been subjected to device processing is placed in a processing container and used as a target. In addition, as Si used as a target, sputtering may be performed on single crystal Si.

Also, in the above examples, sputtering is performed using high-frequency energy using a parallel plate type device for performing plasma etching, but not limited thereto, energy that provides at least partial ionization of an inert gas may be used. For example, the energy is not limited to high-frequency energy, and microwave energy or the like may be used. In addition, in the case of using high-frequency energy, unlike the above-mentioned parallel plates, a method of applying high-frequency power to an antenna to form an induced electromagnetic field may also be used.

Also, the method of forming the Si-containing layer 213 on the surface of the mask layer 212 is not limited to sputtering. For example, the Si-containing layer 213 may be formed on the surface of the mask layer 212 by CVD. When forming the Si-containing layer 213 by CVD, an organic silane-based gas or an inorganic silane-based gas can be used as the gas constituting the raw material, but the inorganic silane-based gas is preferable. CVD at this time can be performed conventionally using these gases.

As a method of forming the Si-containing layer 213 on the surface of the mask layer 212, a method of adding a Si compound such as SiF ₄ to the etching gas may also be employed. Thereby, the improvement of the plasmonic properties of the mask layer 212 made of ArF resist or F2 resist and the etching of the etching target layer 211 can be simultaneously performed.

In addition, in this embodiment, the layer to be etched is not limited to the aforementioned Si oxide, and various materials such as SiC, SiN, organic low dielectric, SiOF, metals, and metal compounds are also applicable. However, since the layer formed on the surface of the mask layer contains Si as a main component, it is difficult to apply it to a target object whose etching target layer is Si. This is because the etching rate is substantially the same when the surface of the mask layer and the layer to be etched are made of the same material. In addition, as the mask layer, it is not limited to photoresist materials with low plasma resistance such as ArF photoresist or F2 photoresist, and can be other organic photoresist layers, and is not limited to photoresist, and can also be other mask layers.

Claims (170)

1, a kind of method of plasma processing is characterized in that, has following operation:

Preparation surface has the handled object of organic layer; With

To described handled object irradiation H ₂Plasma, the plasma-resistance of described organic layer is improved.

2, method of plasma processing according to claim 1 is characterized in that:

Described organic layer is a mask layer.

3, method of plasma processing according to claim 2 is characterized in that:

Described mask layer is a photoresist layer.

4, method of plasma processing according to claim 3 is characterized in that:

Described photoresist layer is made of ArF photoresist or F2 photoresist.

5, a kind of method of plasma processing is characterized in that, has following operation:

Preparation surface has the handled object of organic layer; With

Comprise H to described handled object irradiation ₂With the plasma of the processing gas of inert gas, the plasma-resistance of described organic layer is improved.

6, method of plasma processing according to claim 5 is characterized in that:

Described organic layer is a mask layer.

7, method of plasma processing according to claim 6 is characterized in that:

Described mask layer is a photoresist layer.

8, method of plasma processing according to claim 7 is characterized in that:

Described photoresist layer is made of ArF photoresist or F2 photoresist.

9, method of plasma processing according to claim 5 is characterized in that:

Described processing gas comprises N ₂

10, a kind of method of plasma processing is characterized in that, has following operation:

Preparation surface has the handled object of organic layer; With

Comprise the plasma of material with H and the processing gas of inert gas to the irradiation of described handled object, make the plasma-resistance raising of described organic layer.

11, method of plasma processing according to claim 10 is characterized in that:

Described organic layer is a mask layer.

12, method of plasma processing according to claim 11 is characterized in that:

Described mask layer is a photoresist layer.

13, method of plasma processing according to claim 10 is characterized in that:

The material of the described H of having is NH ₃

14, method of plasma processing according to claim 10 is characterized in that:

Described processing gas comprises N ₂

15, a kind of method of plasma processing is characterized in that, has following operation:

Preparation surface has the handled object of the photoresist layer that is made of ArF photoresist or F2 photoresist; With

Comprise the plasma of the processing gas of material to the irradiation of described handled object, the plasma-resistance of described photoresist layer is improved with H.

16, method of plasma processing according to claim 15 is characterized in that:

The material of the described H of having is H ₂

17, method of plasma processing according to claim 15 is characterized in that:

The material of the described H of having is NH ₃

18, method of plasma processing according to claim 15 is characterized in that:

Described processing gas comprises N ₂

19, method of plasma processing according to claim 15 is characterized in that:

Shine in the atmosphere gas of operation below pressure is 13.3Pa (100mTorr) of described plasma and implement.

20, method of plasma processing according to claim 19 is characterized in that:

The operation of shining described plasma is implemented in pressure is the atmosphere of 1.1-4.0Pa (8-30mTorr).

21, method of plasma processing according to claim 19 is characterized in that:

Described handled object has etching object layer below described photoresist layer, described photoresist has patterns of openings, behind the described plasma of irradiation, and through the described patterns of openings of described photoresist layer, the described etching object layer of plasma etching.

22, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, and this handled object has etch target portion and covers this etch target portion, is formed with the organic layer of patterns of openings;

Plasmaization comprises the processing gas of the material with H in described container handling, shines this plasma to described organic layer; With

Plasma etching gas in described container handling, by described patterns of openings, the described etch target of etching portion.

23, method of plasma processing according to claim 22 is characterized in that:

The material of the described H of having is H ₂

24, method of plasma processing according to claim 22 is characterized in that:

The material of the described H of having is NH ₃

25, method of plasma processing according to claim 22 is characterized in that:

Described processing gas comprises N ₂

26, method of plasma processing according to claim 22 is characterized in that:

Described organic layer is a mask layer.

27, method of plasma processing according to claim 26 is characterized in that:

Described mask layer is a photoresist layer.

28, method of plasma processing according to claim 27 is characterized in that:

Described photoresist layer is made of ArF photoresist or F2 photoresist.

29, method of plasma processing according to claim 22 is characterized in that:

Described processing gas and described etching gas are same gas.

30, method of plasma processing according to claim 22 is characterized in that:

Described etching gas is the gas that has added other gas in described processing gas.

31, method of plasma processing according to claim 22 is characterized in that:

Described etch target portion is SiO ₂Layer.

32, method of plasma processing according to claim 31 is characterized in that:

Described etching gas is to comprise C ₅F ₈Gas.

33, method of plasma processing according to claim 22 is characterized in that:

Shine in the atmosphere of operation below pressure is 13.3Pa (100mTorr) of described plasma and implement.

34, method of plasma processing according to claim 33 is characterized in that:

The operation of shining described plasma is implemented in pressure is the atmosphere of 1.1-4.0Pa (8-30mTorr).

35, a kind of method of plasma processing is characterized in that, has following operation:

Preparation surface has the handled object of the photoresist layer that is made of ArF photoresist or F2 photoresist; With

Comprise the plasma of the processing gas of material to the irradiation of described handled object, the plasma-resistance of described photoresist is improved with H.

36, method of plasma processing according to claim 35 is characterized in that:

The material of the described N of having is N ₂

37, method of plasma processing according to claim 35 is characterized in that:

The material of the described N of having is NH ₃

38, method of plasma processing according to claim 35 is characterized in that:

Described processing gas comprises the material with H.

39, according to the described method of plasma processing of claim 38, it is characterized in that:

The material of the described H of having is from H ₂, CHF ₃, CH ₂F ₂, CH ₃Select among the F more than one.

40, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etch target portion, cover this etch target portion prevent the reflector and cover this prevent the reflector, be formed with the ArF photoresist of patterns of openings or the photoresist layer that the F2 photoresist constitutes;

In described container handling, import and handle gas;

The described processing gas of plasmaization; With

Make this plasma act on described handled object, when making the plasma-resistance raising of described photoresist layer, by described patterns of openings, the described reflector that prevents of etching.

41, according to the described method of plasma processing of claim 40, it is characterized in that:

Described processing gas comprises H ₂

42, according to the described method of plasma processing of claim 41, it is characterized in that:

Described handled object is loaded on the pedestal that is configured in the described container handling, makes described action of plasma in the operation of described handled object, to described pedestal provide 100MHz with upper frequency high frequency power and 3MHz with the high frequency power of upper frequency.

43, according to the described method of plasma processing of claim 42, it is characterized in that:

Described 3MHz is below the 100W with the high frequency power of upper frequency.

44, according to the described method of plasma processing of claim 41, it is characterized in that:

Described processing gas is by H ₂Constitute.

45, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, and this handled object has etching object layer, covers preventing the reflector and covering the mask layer that this prevents the reflector, is formed with patterns of openings of this etching object layer;

In described container handling, import and comprise H ₂Processing gas;

The described processing gas of plasmaization; With

By the patterns of openings of described mask layer, by described plasma selectively to the described reflector that prevents of described mask layer etching.

46, according to the described method of plasma processing of claim 45, it is characterized in that:

Described handled object is loaded on the pedestal that is configured in the described container handling, in described etching work procedure, 100MHz is put on the described pedestal with the high frequency power and the 3MHz of upper frequency so that the high frequency power of upper frequency is overlapping.

47, according to the described method of plasma processing of claim 46, it is characterized in that:

Described 3MHz is below the 100W with the high frequency power of upper frequency.

48, according to the described method of plasma processing of claim 45, it is characterized in that:

Described mask layer is ArF photoresist layer or F2 photoresist layer.

49, according to the described method of plasma processing of claim 45, it is characterized in that:

Described processing gas is by H ₂Constitute.

50, according to the described method of plasma processing of claim 49, it is characterized in that:

After the described operation that prevents the reflector of etching, also has following operation, i.e. plasma CF ₄With H ₂, by the patterns of openings of described mask layer, the described etching object layer of etching is to midway; After the operation that is etched at this midway, plasma etching gas, and the remainder of the described etching object layer of etching.

51, according to the described method of plasma processing of claim 50, it is characterized in that:

Described mask layer is ArF photoresist layer or F2 photoresist layer.

52, according to the described method of plasma processing of claim 50, it is characterized in that:

Described mask layer is made of methacrylic resin.

53, according to the described method of plasma processing of claim 50, it is characterized in that:

Described etching gas is and CF ₄With H ₂Mist other gas is arranged.

54, according to the described method of plasma processing of claim 50, it is characterized in that:

Described etching object layer is SiO ₂Layer,

Described etching gas is to comprise C ₅F ₈With O ₂Gas.

55, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is loaded on the loading stage, and this handled object has etching object layer and mask layer, and this mask layer covers this etching object layer, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

The initial etch operation, plasma CF ₄With H ₂, by the patterns of openings of described mask layer, the described etching object layer of etching is to midway; With

Main etching work procedure, after this initial etch operation, plasmaization comprises the etching gas of fluorocarbon, and the described etching object layer of etching.

56, according to the described method of plasma processing of claim 55, it is characterized in that:

Described etching object layer is SiO ₂Layer.

57, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is loaded on the loading stage, this handled object has etching object layer, cover this etching object layer prevent reflector and mask layer, this mask layer covers this and prevents the reflector, is formed with patterns of openings, is made of acrylic resin;

First etching work procedure, plasma CF ₄, by the patterns of openings of described mask layer, the described reflector that prevents of etching;

Second etching work procedure, plasma CF ₄With H ₂, by the patterns of openings of described mask layer, the described etching object layer of etching is to midway; With

The 3rd etching work procedure, after this second etching work procedure, plasmaization comprises the etching gas of fluorocarbon, and the described etching object layer of etching.

58, according to the described method of plasma processing of claim 57, it is characterized in that:

Described etching object layer is SiO ₂Layer.

59, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is loaded on the pedestal that is configured in the container handling, and this handled object has etching object layer and covers this etching object layer, is formed with the mask layer of opening;

In described container handling, import and comprise H ₂Processing gas;

To described pedestal provide 100MHz with upper frequency high frequency power and 3MHz with the high frequency power of upper frequency; With

Pressure in the described container handling is dropped to below the 13.3Pa (100mTorr).

60, according to the described method of plasma processing of claim 59, it is characterized in that:

Described 3MHz is below the 100W with the high frequency power of upper frequency.

61, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, and this handled object has etch target portion and photoresist layer, and this photoresist layer covers this etch target portion, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

Plasmaization comprises the processing gas of the material with N in described container handling, and shines described photoresist layer; With

Plasma etching gas in described container handling, by described patterns of openings, the described etch target of etching portion.

62, according to the described method of plasma processing of claim 61, it is characterized in that:

The material of the described N of having is N ₂

63, according to the described method of plasma processing of claim 62, it is characterized in that:

Described processing gas comprises H ₂

64, according to the described method of plasma processing of claim 62, it is characterized in that:

Described processing gas comprises from by CHF ₃, CH ₂F ₂, CH ₃More than a kind of selection among the group that F constitutes.

65, according to the described method of plasma processing of claim 61, it is characterized in that:

The material of the described N of having is NH ₃

66, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etch target portion, cover this etch target portion prevent reflector and photoresist layer, this photoresist layer covers this and prevents the reflector, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

First etching work procedure, plasmaization comprises the processing gas of the material with N in described container handling, and by described patterns of openings, the described reflector that prevents of etching; With

Second etching work procedure, plasma etching gas in described container handling, by described patterns of openings, the described etch target of etching portion.

67, according to the described method of plasma processing of claim 66, it is characterized in that:

The material of the described N of having is N ₂

68, according to the described method of plasma processing of claim 67, it is characterized in that:

Described processing gas comprises H ₂

69, according to the described method of plasma processing of claim 68, it is characterized in that:

Pressure in the described container handling is become 107-160Pa (800-1200mTorr) implement described first etching work procedure.

70, according to the described method of plasma processing of claim 69, it is characterized in that:

Described etching object layer is SiO ₂Layer, described etching gas comprises C ₅F ₈

71, according to the described method of plasma processing of claim 70, it is characterized in that:

Described C ₅F ₈Be 1,1,1,4,4,5,5,5-octafluoro-valerylene.

72, according to the described method of plasma processing of claim 67, it is characterized in that:

Described processing gas comprises from by CHF ₃, CH ₂F ₂, CH ₃More than a kind of selection among the group that F constitutes.

73, according to the described method of plasma processing of claim 66, it is characterized in that:

The material of the described N of having is NH ₃

74, according to the described method of plasma processing of claim 66, it is characterized in that:

Described etching object layer is SiO ₂Layer, described etching gas comprises C ₄F ₆

75, according to the described method of plasma processing of claim 66, it is characterized in that:

Described etching object layer is SiO ₂Layer, described etching gas comprises C ₅F ₈

76, according to the described method of plasma processing of claim 75, it is characterized in that:

Described C ₅F ₈It is straight chain C ₅F ₈

77, according to the described method of plasma processing of claim 76, it is characterized in that:

Described straight chain C ₅F ₈Be 1,1,1,4,4,5,5,5-octafluoro-valerylene.

78, according to the described method of plasma processing of claim 75, it is characterized in that:

Described processing gas comprises N ₂With H ₂, the pressure in the described container handling is become 107-160Pa (800-1200mTorr) implements described first etching work procedure.

79, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etching object layer and organic mask layer, this organic mask layer covers described etching object layer, is formed with patterns of openings, and this container handling comprises the component parts of the exposed division that has the material that comprises Si;

In described container handling, import from H ₂, N ₂At least a processing gas of selecting among the group who constitutes with He; With

The described processing gas of plasmaization, the described organic mask layer of plasma treatment.

80, according to the described method of plasma processing of claim 79, it is characterized in that:

After described plasma treatment operation, also has the etched operation of carrying out described etching object layer.

81, according to the described method of plasma processing of claim 79, it is characterized in that:

Described organic mask layer is the organic photoresist layer.

82,1 described method of plasma processing according to Claim 8 is characterized in that:

Described organic photoresist layer is made of ArF photoresist or F2 photoresist.

83, according to the described method of plasma processing of claim 79, it is characterized in that:

The material of the described Si of comprising is made of single crystalline Si.

84, according to the described method of plasma processing of claim 79, it is characterized in that:

The material of the described Si of comprising is made of SiC.

85, according to the described method of plasma processing of claim 79, it is characterized in that:

The described component parts that has the exposed division of the material that comprises Si is arranged on the counter electrode of the handled object in the described container handling.

86, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etching object layer, covers the organic membrane and the organic mask layer of described etching object layer, this organic mask layer covers described organic membrane, be formed with patterns of openings, this container handling comprises the component parts of the exposed division that has the material that comprises Si;

In described container handling, import etching gas;

The described etching gas of plasmaization, by the patterns of openings of described organic mask layer, the described organic membrane of etching;

In described container handling, import from H ₂, N ₂At least a processing gas of selecting among the group who constitutes with He; With

The described processing gas of plasmaization, the described organic mask layer of plasma treatment.

87,6 described method of plasma processing according to Claim 8 is characterized in that:

Described etching gas comprises CF ₄

88,6 described method of plasma processing according to Claim 8 is characterized in that:

After described plasma treatment operation, also has the etched operation of carrying out described etching object layer.

89,6 described method of plasma processing according to Claim 8 is characterized in that:

Described organic membrane is organic reflectance coating that prevents.

90,6 described method of plasma processing according to Claim 8 is characterized in that:

Described organic mask layer is the organic photoresist layer.

91, according to the described method of plasma processing of claim 90, it is characterized in that:

Described organic photoresist layer is made of ArF photoresist or F2 photoresist.

92,6 described method of plasma processing according to Claim 8 is characterized in that:

The material of the described Si of comprising is made of single crystalline Si.

93,6 described method of plasma processing according to Claim 8 is characterized in that:

The material of the described Si of comprising is made of SiC.

94,6 described method of plasma processing according to Claim 8 is characterized in that:

The described component parts that has the exposed division of the material that comprises Si is arranged on the counter electrode of the handled object in the described container handling.

95, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etching object layer, covers the organic membrane and the organic mask layer of described etching object layer, this organic mask layer covers described organic membrane, be formed with patterns of openings, this container handling comprises the component parts of the exposed division that has the material that comprises Si;

In described container handling, import H ₂With

The H of plasma importing ₂, by the patterns of openings of described organic mask layer, the described organic membrane of etching.

96, according to the described method of plasma processing of claim 95, it is characterized in that:

After the operation of the described organic membrane of etching, also has the etched operation of carrying out described etching object layer.

97, according to the described method of plasma processing of claim 95, it is characterized in that:

Described organic membrane is organic reflectance coating that prevents.

98, according to the described method of plasma processing of claim 95, it is characterized in that:

Described organic mask layer is the organic photoresist layer.

99, according to the described method of plasma processing of claim 98, it is characterized in that:

Described organic photoresist layer is made of ArF photoresist or F2 photoresist.

100, according to the described method of plasma processing of claim 95, it is characterized in that:

The material of the described Si of comprising is made of single crystalline Si.

101, according to the described method of plasma processing of claim 95, it is characterized in that:

The material of the described Si of comprising is made of SiC.

102, according to the described method of plasma processing of claim 95, it is characterized in that:

The described component parts that has the exposed division of the material that comprises Si is arranged on the counter electrode of the handled object in the described container handling.

103, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, and this handled object has etching object layer and photoresist layer, and this photoresist layer covers this etching object layer, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

In the container handling that holds described handled object, import and comprise C ₂F ₄Processing gas;

The described processing gas of plasmaization; With

By the patterns of openings of described photoresist layer, come etching object layer in the described handled object of etching by the plasma of described processing gas.

104, according to the described method of plasma processing of claim 103, it is characterized in that:

Described etching object layer is carbon-containing bed.

105, according to the described method of plasma processing of claim 103, it is characterized in that:

Described etching object layer is an organic layer.

106, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, and this handled object has etching object layer and mask layer, and this mask layer covers this etching object layer, is formed with patterns of openings;

In the container handling that holds described handled object, import and comprise C ₂F ₄With O ₂Processing gas;

The described processing gas of plasmaization; With

By the patterns of openings of described mask layer, come etching object layer in the described handled object of etching by the plasma of described processing gas.

107, according to the described method of plasma processing of claim 106, it is characterized in that:

Described mask layer is a photoresist layer.

108, according to the described method of plasma processing of claim 107, it is characterized in that:

Described etching object layer is to prevent the reflector.

109, according to the described method of plasma processing of claim 107, it is characterized in that:

Described photoresist layer is made of ArF photoresist or F2 photoresist.

110, according to the described method of plasma processing of claim 106, it is characterized in that:

Described etching object layer is carbon-containing bed.

111, according to the described method of plasma processing of claim 106, it is characterized in that:

Described etching object layer is an organic layer.

112, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etch target portion, cover this etch target portion prevent reflector and photoresist layer, this photoresist layer covers this and prevents the reflector, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

Plasmaization comprises material with C and F and the etching gas with material of H in described container handling, comes the described reflector that prevents of etching through described patterns of openings; With

The described etch target of etching portion.

113, according to the described method of plasma processing of claim 112, it is characterized in that:

The material of the described H of having is a hydrocarbon.

114, according to the described method of plasma processing of claim 113, it is characterized in that:

Described hydrocarbon is CH ₄

115, according to the described method of plasma processing of claim 112, it is characterized in that:

The material of the described H of having is H ₂

116, according to the described method of plasma processing of claim 112, it is characterized in that:

The material of the described H of having is a hydrofluorocarbons.

117, according to the described method of plasma processing of claim 116, it is characterized in that:

The H atomicity of described hydrofluorocarbons is more than 3 with the ratio of F atomicity.

118, according to the described method of plasma processing of claim 117, it is characterized in that:

Described hydrofluorocarbons is CH ₃F.

119, according to the described method of plasma processing of claim 118, it is characterized in that:

Described CH ₃The flow of F is 0.04-0.07 with the ratio of the mass flow-rate that has C and F described in the described etching gas.

120, according to the described method of plasma processing of claim 112, it is characterized in that:

The material of described C of having and F is CF ₄

121, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etch target portion, cover this etch target portion prevent reflector and mask layer, this mask layer covers this and prevents the reflector, is formed with patterns of openings;

Plasmaization comprises the material with C and F and the etching gas of hydrocarbon in described container handling, comes the described reflector that prevents of etching through described patterns of openings; With

The described etch target of etching portion.

122, according to the described method of plasma processing of claim 121, it is characterized in that:

Described hydrocarbon is CH ₄

123, according to the described method of plasma processing of claim 121, it is characterized in that:

The material of described C of having and F is CF ₄

124, according to the described method of plasma processing of claim 121, it is characterized in that:

Described mask layer is ArF photoresist layer or F2 photoresist layer.

125, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etch target portion, cover this etch target portion prevent reflector and mask layer, this mask layer covers this and prevents the reflector, is formed with patterns of openings;

The atomicity that plasma etching gas in described container handling, this etching gas comprise the material with C and F and have C, H and F and a H and the ratio of the atomicity of F are the material more than 3, come the described reflector that prevents of etching through described patterns of openings; With

The described etch target of etching portion.

126, according to the described method of plasma processing of claim 125, it is characterized in that:

The atomicity of the described C of having, H and F and H and the ratio of the atomicity of F are that the material more than 3 is CH ₃F.

127, according to the described method of plasma processing of claim 125, it is characterized in that:

The material of described C of having and F is CF ₄

128, according to the described method of plasma processing of claim 127, it is characterized in that:

Described CH ₃The ratio that has the mass flow-rate of C and F in the flow of F and the described etching gas is 0.04-0.07.

129, according to the described method of plasma processing of claim 125, it is characterized in that:

Described mask layer is ArF photoresist layer or F2 photoresist layer.

130, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, and this handled object has etch target portion and photoresist layer, and this photoresist layer covers this etch target portion, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

Plasmaization comprises material with C and F and the processing gas of CO in described container handling, shines this plasma to described photoresist layer; With

Plasma etching gas in described container handling through described patterns of openings, comes the described etch target of etching portion by this plasma.

131, according to the described method of plasma processing of claim 130, it is characterized in that:

The material of described C of having and F is CF ₄

132, according to the described method of plasma processing of claim 130, it is characterized in that:

Described processing gas and described etching gas are same gas.

133, according to the described method of plasma processing of claim 132, it is characterized in that:

Described etch target portion prevents the reflector.

134, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etch target portion, cover this etch target portion prevent reflector and photoresist layer, this photoresist layer covers this and prevents the reflector, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

First etching work procedure, plasmaization comprises material with C and F and first etching gas of CO in described container handling, through described patterns of openings, comes the described reflector that prevents of etching by this plasma; With

Second etching work procedure, plasmaization second etching gas in described container handling through described patterns of openings, comes the described etch target of etching portion by this plasma.

135, according to the described method of plasma processing of claim 134, it is characterized in that:

The material of described C of having and F is CF ₄

136, according to the described method of plasma processing of claim 134, it is characterized in that:

Described etch target portion is SiO ₂Layer, described second etching gas comprises C ₅F ₈

137, according to the described method of plasma processing of claim 134, it is characterized in that:

Described etch target portion is SiO ₂Layer, described second etching gas comprises C ₄F ₆

138, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etch target portion, cover etch target portion prevent reflector and mask layer, this mask layer covers this and prevents the reflector, is formed with patterns of openings;

First etching work procedure, plasmaization comprises CF in described container handling ₄With first etching gas of CO,, come the described reflector that prevents of etching by this plasma through described patterns of openings; With

Second etching work procedure, plasmaization second etching gas in described container handling through described patterns of openings, comes the described etch target of etching portion by this plasma.

139, according to the described method of plasma processing of claim 138, it is characterized in that:

Described etch target portion is SiO ₂Layer, described second etching gas comprises C ₄F ₆

140, according to the described method of plasma processing of claim 139, it is characterized in that:

Described etch target portion is SiO ₂Layer, described second etching gas comprises C ₅F ₈

141, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is configured in the container handling, this handled object has etching object layer, covers the organic reflector and photoresist layer of preventing of this etching object layer, this photoresist layer covers this organic reflector that prevents, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

In this container handling, import etching gas with the material that comprises Si; With

This etching gas of plasmaization, by the patterns of openings of described photoresist layer, the organic reflector that prevents of etching.

142, according to the described method of plasma processing of claim 141, it is characterized in that:

The material of the described Si of comprising is SiF ₄

143, according to the described method of plasma processing of claim 142, it is characterized in that:

Described etching gas contains CHF ₃

144, according to the described method of plasma processing of claim 142, it is characterized in that:

Described etching gas contains HBr.

145, according to the described method of plasma processing of claim 142, it is characterized in that:

Described etching gas contains He.

146, according to the described method of plasma processing of claim 142, it is characterized in that:

Described etching gas contains H ₂

147, according to the described method of claim 141, it is characterized in that:

After the described organic operation that prevents the reflector of etching, also has the operation of coming the described etching object layer of plasma etching by the patterns of openings of described ArF photoresist layer.

148, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is loaded on the pedestal that is arranged in container handling, and this handled object has etch target portion and covers this etching object layer, is formed with the mask layer of opening;

Having the described handled object and at least a portion on surface in described container handling is under the parts of Si, imports inert gas in described container handling;

The high-frequency energy of at least a portion of the described inert gas of ionization is provided in described container handling;

In described container handling, import etching gas;

This etching gas of plasmaization; With

In described container handling,, come the described etching object layer of etching by the plasma of described etching gas by the patterns of openings of described mask layer.

149, according to the described method of plasma processing of claim 148, it is characterized in that:

Described mask layer is ArF photoresist layer or F2 photoresist layer.

150, according to the described method of plasma processing of claim 148, it is characterized in that:

The parts that described surperficial at least a portion is Si are to be positioned at described handled object focusing ring on every side.

151, according to the described method of plasma processing of claim 148, it is characterized in that:

The parts that described surperficial at least a portion is Si are that described etching gas is imported spray head in the described container handling.

152, according to the described method of plasma processing of claim 148, it is characterized in that:

Described etching object layer is the Si oxide, and described etching gas comprises from by C ₄F ₆, C ₄F ₈And C ₅F ₈Select among the group who constitutes at least a kind.

153, according to the described method of plasma processing of claim 148, it is characterized in that:

After described etching work procedure, also has the operation that the multistage plasma is removed mask layer.

154, according to the described method of plasma processing of claim 153, it is characterized in that:

The operation that described multistage plasma is removed described mask layer has: first removes operation, removes the part of mask layer with the plasma of the gas that comprises fluorine compounds; With the second removal operation, remove at least a portion of remaining mask layer in the first removal operation with the plasma of the gas that does not comprise fluorine compounds.

155, according to the described method of plasma processing of claim 154, it is characterized in that:

Described mask layer is the ArF photoresist layer, and the gas that uses in the described first removal operation is CF ₄

156, according to the described method of plasma processing of claim 148, it is characterized in that:

Describedly energy is imported operation in the described container handling comprise to the antenna that is arranged on outside the described container handling and apply high frequency power.

157, according to the described method of plasma processing of claim 148, it is characterized in that:

Describedly energy is imported the counter electrode that operation in the described container handling comprises the described pedestal in being arranged on described container handling apply high frequency power.

158, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is loaded on the pedestal that is arranged in container handling, and this handled object has etching object layer and mask layer, and this mask layer covers this etching object layer, is formed with patterns of openings;

In described container handling, form Si on described mask layer surface and contain layer;

In described container handling, import etching gas;

The described etching gas of plasmaization; With

In described container handling,, come the described etching object layer of etching by the plasma of described etching gas by the patterns of openings of described mask layer.

159, according to the described method of plasma processing of claim 158, it is characterized in that:

After the operation of described plasma etching, also has the operation that the multistage plasma is removed mask layer.

160, according to the described method of plasma processing of claim 159, it is characterized in that:

The operation that described multistage plasma is removed described mask layer has: first removes operation, removes the part of mask layer with the plasma of the gas that comprises fluorine compounds; With the second removal operation, remove at least a portion of remaining mask layer in the first removal operation with the plasma of the gas that does not comprise fluorine compounds.

161, according to the described method of plasma processing of claim 160, it is characterized in that:

Described mask layer is ArF photoresist layer or F2 photoresist layer, and the gas that uses in the described first removal operation is CF ₄

162, according to the described method of plasma processing of claim 158, it is characterized in that:

Described mask layer is ArF photoresist layer or F2 photoresist layer.

163, according to the described method of plasma processing of claim 158, it is characterized in that:

Described etching object layer is the Si oxide, and described etching gas comprises from C ₄F ₆, C ₄F ₈, C ₅F ₈Middle at least a kind of selecting.

164, according to the described method of plasma processing of claim 158, it is characterized in that:

Implement to form the operation that described Si contains layer by the PVD method.

165, according to the described method of plasma processing of claim 158, it is characterized in that:

Implement to form the operation that described Si contains layer by the CVD method.

166, a kind of method of plasma processing is characterized in that, has following operation:

Prepare container handling, at least a portion that the surface is set in inside be parts, first electrode of Si and be positioned at this first electrode relative position on second electrode;

Load handled object on described first electrode in described container handling, this handled object has etching object layer and mask layer, and this mask layer covers this etching object layer, is formed with patterns of openings;

In described container handling, import inert gas;

Apply high frequency power to described first electrode;

Apply high frequency power to described second electrode;

Import etching gas to described container handling; With

In described container handling,, come the described etching object layer of etching by the etching gas that utilizes described high frequency power plasmaization by the patterns of openings of described mask layer.

167, according to the described method of plasma processing of claim 166, it is characterized in that:

At least a portion on described surface is that the parts of Si are the battery lead plate of described second electrode.

168, according to the described method of plasma processing of claim 166, it is characterized in that:

After the operation of described plasma etching, also has the operation that the multistage plasma is removed mask layer.

169, a kind of method of plasma processing is characterized in that, has following operation:

Handled object is loaded on the pedestal that is arranged in container handling, and this handled object has etching object layer and photoresist layer, and this photoresist layer covers this etching object layer, is formed with patterns of openings, is made of ArF photoresist or F2 photoresist;

In described container handling, import the etching gas that comprises the Si compound;

The described etching gas of plasmaization; With

In described container handling,, come the described etching object layer of etching by the plasma of described etching gas by the patterns of openings of described photoresist layer.

170, according to the described method of plasma processing of claim 169, it is characterized in that:

Described Si compound is SiF ₄

Images