TW200401365A - Plasma processing method - Google Patents

Abstract

The present invention relates to a plasma processing method, which comprises: the operation to prepare the processed body having an organic layer on the surface, and the operation to enhance the plasma-endurance of the organic layer by irradiating H2 plasma onto the processed body.

Description

200401365 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a plasma processing method performed in a semiconductor device manufacturing operation [prior art] When performing plasma etching on an etching target layer, Use a resist mask such as a photoresist. Especially recently, in order to meet the requirements of microfabrication, in order to form an opening pattern below about 0 · 1 3 # m, an appropriate ArF photoresist or F2 photoresist, that is, ArF gas or F2 gas is often used. It is used as a photoresist for exposing laser light as a light source. However, the 'ArF photoresist layer or F2 photoresist layer is low in plasma resistance, and therefore, there is a problem that the surface of the photoresist layer is cracked during etching. Because the surface of the photoresist layer is wrinkled, the shape of the openings is changed 'at the same time as the etching progresses, and an etched hole or etched trench of a designed shape cannot be formed. In addition, the portion where the photoresist layer disappeared during the etching was also etched at the portion where the etching was not originally intended. As a method for improving the plasma resistance of the photoresist layer, there are methods of irradiating ultraviolet rays, electron beams, or ion beams on the surface of the photoresist layer (Japanese Patent Application Laid-Open No. 60-110124, Japanese Patent Application Laid-Open No. 2-252233). Gazette, Japanese Patent Application Laid-Open No. 57-157523), a method for heat curing a photoresist (Japanese Patent Laid-Open No. 4-2 3 4 2 5) or applying heat or light energy to an organic Si compound A method for coating a thin hardened layer on the surface of the photoresist (2) (2) 200401365 layer (Japanese Patent Application Laid-Open No. 2-40914). In the aforementioned method for improving the plasma resistance of the photoresist layer, it is necessary to perform a treatment for improving the plasma resistance in a container different from the container used in the subsequent etching operation. The transfer of the object to be etched from a container that has been improved in the resistance to the plasma of the photoresist layer results in a decrease in the yield of the transfer operation or a decrease in production efficiency due to the transfer time. In addition, providing a container which is different from the etching container for improving the plasma resistance not only requires extra space, but also leads to an increase in cost. In addition, instead of providing a container for improving the plasma resistance of the etching container, an ultraviolet irradiation means or heating means may be added to the etching vessel. However, the ultraviolet irradiation means or heating means are still required, and costs are still caused. rise. On the other hand, when the melting target portion is directly covered by the photoresist layer, the photoresist layer is exposed and developed later to form an opening pattern, which reduces the design dimensional accuracy of the opening pattern. Therefore, an anti-reflection layer is interposed between the etching target portion and the photoresist layer. Proposal: The anti-reflection layer is etched by a plasma containing a gas having a substance of C and F, such as a mixed gas of C4F8 and 02, a mixed gas of HBr, CF4, and He, and a mixed gas of CH2F2, CF4, and He ( Japanese Patent Application Laid-Open No. 10-26 1 62). Also known as an etching gas system for the anti-reflection layer is a mixed gas of, for example, CF4 and 02 (Japanese Patent Application Laid-Open No. 7-307328). However, in a state where the antireflection layer is etched by a plasma of a mixed gas of C4F8 and 〇2 or a mixture of CF4 and 〇7- (3) (3) 200401365, the surface of the ArF photoresist layer is Wrinkles also occur, or vertical streaks occur in the ArF photoresist layer, or a considerable amount of the ArF photoresist layer that becomes the mask layer is also etched, and cannot function as a mask. [Summary of the Invention] [Disclosure of the Invention] The object of the present invention is to provide an etching resistance of an organic layer such as an ArF photoresist layer, which does not cause a decrease in yield or a decrease in production efficiency and does not cause an increase in cost. Plasma treatment method. In addition, the present invention provides a plasma processing method capable of improving the etching resistance of an organic layer and performing plasma etching. In addition, the present invention provides an electric paddle resistance that can highly maintain a cover layer such as an ArF photoresist layer or an F2 photoresist layer when etching an anti-reflection layer or an etching target layer of a substrate thereof. Plasma treatment method. In addition, the present invention provides a method for suppressing surface cracking of a mask layer such as an ArF photoresist layer or an F2 photoresist layer, while maintaining a good etching selection ratio, and performing uranium etch at a high etching rate. An electric paddle treatment method for an anti-reflection layer of a material or an etching target layer. According to the first aspect of the present invention, a plasma processing method is provided, which includes a work of preparing a processed object having an organic layer on a surface, and irradiating the processed object with a plasma to improve the organic layer. Plasma resistance operation. -8- (4) (4) 200401365 According to the second aspect of the present invention, a plasma treatment method is provided to 'have the work of preparing a processed object having an organic layer on the surface, and the above-mentioned processed object. Plasma irradiation with a processing gas containing H2 and an inert gas to improve the plasma resistance of the organic layer. According to the third aspect of the present invention, a plasma treatment method is provided, which includes: preparing an object to be treated with an organic layer on the surface; and irradiating the object to be treated with a substance containing tritium and an inert gas. Plasma processing gas to improve the plasma resistance of the organic layer. According to the fourth aspect of the present invention, there is provided a plasma processing method comprising the steps of preparing a surface-treated object having a photoresist layer composed of an ArF photoresist or an F2 photoresist on a surface, and a process for The object to be treated is irradiated with a plasma containing a processing gas having a substance containing tritium to improve the plasma resistance of the photoresist layer. According to the fifth aspect of the present invention, there is provided a plasma processing method including the operation of arranging a processing object having an etching target portion and an organic layer covering the etching target portion to form an opening pattern in a processing container. ; In the aforementioned processing container, plasma processing is performed on a process gas containing a substance having tritium, and in the aforementioned organic layer, the plasma is irradiated; and in the aforementioned processing container, plasma etching is performed on the etching gas; The etching operation is performed on the etching target portion through the opening pattern. According to the sixth aspect of the present invention, there is provided a plasma treatment method including: preparing, on a surface, a photoresist layer composed of an ArF photoresist or F2 photo-9- (5) 200401365 resist; And the operation of improving the plasma resistance of the photoresist layer by irradiating the plasma of the treatment object with a treatment gas containing a substance having N.

According to the seventh aspect of the present invention, there is provided a plasma processing method including an ArF photoresist having an etching target portion, an antireflection layer covering the etching target portion, and an opening pattern formed by covering the antireflection layer. A photoresist layer composed of a photoresist or an F2 photoresist, disposed in a processing container; introducing a processing gas into the processing container; and performing plasma processing on the processing gas; and The plasma is applied to the object to be treated to improve the plasma resistance of the photoresist layer, and at the same time, the anti-reflection layer is etched through the opening pattern.

According to the eighth aspect of the present invention, there is provided a plasma processing method 'having: in a processing container, an etching target layer is disposed' to cover the anti-reflection layer covering the etching target layer and covering the anti-reflection layer to form an opening pattern Operation of the object to be treated in the cover layer; operation of introducing a processing gas containing H2 into the processing container; plasma processing of the processing gas; and passing the cover through the plasma The opening pattern of the curtain layer enables the anti-reflection layer to selectively etch the cover curtain layer. According to the ninth aspect of the present invention, a plasma processing method is provided. The method includes a mask formed of an ArF photoresist or an F2 photoresist having an etching target layer and an opening pattern covering the etching target layer. The object to be treated in the curtain layer is placed on the mounting table. For cf4 and H2, -10- (6) (6) 200401365 lines are plasmatized, and for the etching target layer through the opening pattern of the mask layer, The initial etching operation until the middle of the process: and after this initial etching operation, plasma etching is performed on the etching gas containing fluorocarbon, and the main etching operation is performed to etch the aforementioned etching target layer. According to the tenth aspect, a plasma processing method is provided, which comprises an etching target layer, an anti-reflection layer covering the etching target layer, and a mask made of acrylic resin to form an opening pattern covering the anti-reflection layer. Layer to-be-processed object; placing c F4 into plasma, and feeding the anti-reflection layer through the opening pattern of the cover layer. The first etching operation of etching; the second etching operation of plasma etching of CF4 and H2, and the etching of the etching target layer through the opening pattern of the mask layer, until the middle of the etching operation; and (2) After the etching operation, plasma etching is performed on an etching gas containing fluorocarbon, and a third etching operation is performed to etch the aforementioned etching target layer. According to the eleventh aspect of the present invention, there is provided a plasma processing method including: placing a sensor having an etching target layer on a sensor disposed in a processing container, and forming a cover covering the etching target layer to form an opening. Work of layered objects to be processed; operation of introducing a processing gas containing H2 into the aforementioned processing container; operation of supplying high-frequency power at frequencies above 100 MHz and high-frequency power at frequencies above 3 MHz in the aforementioned sensors; and ' The operation to make the pressure in the processing container be 13.3 Pa (100 mTorr) or less. According to the twelfth aspect of the present invention, an electric award -11-(7) (7) 200401365 processing method is provided, which includes an ArF light having an etching target portion and forming an opening pattern covering the etching target portion. The object to be processed in the mask layer composed of a resist or F2 photoresist is placed in a processing container; in the aforementioned processing container, a processing gas containing a substance having N is plasmatized and irradiated on The operation of the photoresist layer; and the plasma treatment of an etching gas in the processing container, and the etching operation of the t-worm-etched part through the opening pattern. According to the thirteenth aspect of the present invention, there is provided a plasma processing method including: forming an antireflection layer having an etching target portion, covering the etching target portion, and forming an opening pattern covering the antireflection layer; The object to be processed with a photoresist layer composed of F photoresist or F 2 photoresist is disposed in a processing container; in the foregoing processing container, a processing gas containing a substance having N is plasmatized A first etching operation for etching the anti-reflection layer through the opening pattern; and plasma-etching the etching gas in the processing container, and using the opening pattern for the etching target portion, The second uranium etching operation is performed. According to the fourteenth aspect of the present invention, there is provided a plasma processing method comprising: arranging a processed object having an etching target layer and an organic mask layer forming an opening pattern covering the etching target layer, the target body including Operations in the processing container of the constituent members of the substance exposed portion of Si; introduction of at least one processing gas selected from the group consisting of H2, N2, and He into the processing container; and Plasma treatment is performed, and plasma treatment is performed on the aforementioned organic cover curtain layer. (12) (8) (8) 200401365. According to the fifth aspect of the present invention, an electric award processing method is provided. The method includes: an organic film having an etching target layer, an organic film covering the etching target layer, and an organic mask layer forming an opening pattern covering the organic film. The object to be processed is disposed in a processing container provided with a constituent member containing a substance exposed portion of Si. The operation of introducing an etching gas into the processing container is performed by plasma forming the etching gas through the organic mask. Layer opening pattern for the organic film to perform ageing operations; to introduce at least one processing gas selected from the group consisting of H2, N2, and He into the processing container; and for the foregoing Plasma treatment is performed by processing gas, and plasma treatment is performed on the organic cover layer. According to the sixteenth aspect of the present invention, there is provided a plasma processing method including: an organic film having an etching target layer, an organic film covering the etching target layer, and an organic mask layer forming an opening pattern covering the organic film; The object to be processed is disposed in a processing container having a constituent member containing a substance exposed portion of Si; the operation of introducing H2 into the processing container; and performing plasmaization of the introduced h2 through the organic cover The opening pattern of the curtain layer etches the organic film. According to the seventeenth aspect of the present invention, 'an electric prize processing method is provided, which includes an ArF photoresist or an F2 photoresist with an etching target layer and an opening pattern covering the uranium etching target layer. The photoresist layer of the object to be processed is arranged in the processing container; in the aforementioned collection of 13- (9) (9) 200401365, the processing container containing the object to be processed, the operation of introducing the processing gas containing c2F4; Plasmaization of the processing gas; and 'Electrosification of the 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 the eighteenth aspect of the present invention, there is provided a plasma processing method comprising: arranging a processing object having an etching target layer and a mask layer forming an opening pattern covering the etching target layer in a processing container; The operation of introducing the processing gas containing c2F4 and 02 into the processing container containing the object to be processed; the operation of plasmaizing the processing gas; , By plasma treatment of the gas, such that the etching target layer of the body being treated, etching work is performed through the opening pattern of the mask layer curtain. According to the nineteenth aspect of the present invention, a plasma processing method is provided. The method includes: having an etching target portion, an anti-reflection layer covering the etching target portion, and forming an opening pattern covering the anti-reflection layer, and using ArF light The object to be processed with a photoresist layer composed of a photoresist or F2 photoresist is disposed in a processing container. In the aforementioned processing container, for an etching gas containing a substance having C and F and a substance having η, Performing a plasma operation to etch the anti-reflection layer through the opening pattern; and an operation to etch the etching target portion. According to the twentieth aspect of the present invention, a plasma processing method is provided. The method includes: having an etching target portion, an anti-reflection layer covering the etching target portion, and a mask forming an opening pattern covering the anti-reflection layer- 14-(10) (10) 200401365 layer of the object to be disposed in the processing container; in the aforementioned processing container, the plasma of the etching gas containing substances containing C and F and hydrogen and carbon is transmitted through An operation of etching the anti-reflection layer by the opening pattern; and an operation of etching the etching target portion. According to the twenty-first aspect of the present invention, there is provided a plasma processing method including: an anti-reflection layer having an etching target portion, covering the etching target portion, and a mask layer forming an opening pattern covering the anti-reflection layer. The object to be processed is disposed in a processing container. In the foregoing processing container, for a substance containing C and F and a substance having C, Η, and F, the ratio of the number of Η atoms to the number of F atoms is 値 3 or more. Plasma etching using an etching gas, etching the anti-reflection layer through the opening pattern, and etching the object to be etched. According to the twenty-second aspect of the present invention, there is provided a plasma processing method including a light having an etched portion and forming an opening pattern covering the etched portion, and comprising light consisting of an ArF photoresist or an F2 photoresist. The object to be processed in the resist layer is disposed in a processing container. In the foregoing processing container, an electric treatment is performed on a processing gas containing a substance having C and F and CO. The light is irradiated to the photoresist. An operation of an agent layer; and an operation of plasma-etching an etching gas in the processing container, and using the plasma to etch the etching target portion through the opening pattern. According to the twenty-third aspect of the present invention, there is provided a plasma processing method comprising: forming an antireflection layer having a target portion to be etched, covering the portion to be engraved, and forming an opening pattern covering the antireflection layer; -15- (11) (11) 200401365

The object to be processed of the photoresist layer composed of ArF photoresist or F2 photoresist · Arranged in a processing container; in the aforementioned processing container, the first etching containing a substance having C and F and C 0 Plasma by gas' through the plasma through the opening pattern to perform the first etching operation on the anti-reflection layer; and in the processing container, to perform the plasma on the second etching gas The second etching operation for etching is performed on the etching target portion by the plasma through the opening pattern. According to the twenty-fourth aspect of the present invention, there is provided a plasma processing method comprising: forming a mask layer having an etching target portion, an anti-reflection layer covering the etching target portion, and a mask layer forming an opening pattern covering the anti-reflection layer; The object to be processed is disposed in a processing container. In the processing container, the first etching gas containing CF4 and CO is plasmatized, and the plasma is transmitted through the opening pattern to prevent the reflection. And performing a first etching operation to perform an etching step; and plasma-forming a second etching gas in the processing container, and the plasma is etched through the opening pattern and the etching target portion is etched. The second etching operation. According to the twenty-fifth aspect of the present invention, there is provided a plasma processing method including: forming an organic reflection prevention layer having an etching target layer, covering the etching target layer, and forming an opening pattern covering the organic reflection preventing layer, and ArF photoresist or F2 photoresist layer of the photoresist layer of the object to be processed in the processing container; the processing container, the introduction of the substance containing Si etching gas operation; and, The etching-16- (12) (12) 200401365 etching gas is used for plasma, and the opening pattern of the photoresist layer is used to etch the organic reflection prevention layer. According to the twenty-sixth aspect of the present invention, a plasma processing method is provided, which includes a sensor in a processing container, placing a layer having an etching target layer, and forming a cover covering the etching target layer to form an opening. The operation of the layered object; the operation of introducing an inert gas into the processing container under the structure in which the at least a portion of the object and the surface becomes Si in the processing container; at least a part of the inert gas becomes ions The operation of applying the high-frequency energy converted into the aforementioned processing container; the operation of introducing an etching gas into the aforementioned processing container; the operation of plasmaizing the etching gas: and the plasma of the aforementioned etching gas' In the processing container, an etching operation is performed on the etching target layer through the opening pattern of the cover layer. According to the twenty-seventh aspect of the present invention, there is provided a plasma processing method including a sensor in a processing container, and placing a cover having an etching target layer and a cover covering the etching target layer to form an opening pattern. The operation of the object to be treated in the curtain layer; the operation of forming an Si-containing layer on the surface of the cover layer in the processing container; the operation of introducing an etching gas in the processing container; the electrical operation of the etching gas. The operation of slurrying; and 'the operation of performing etching on the etched object layer through the opening pattern of the mask layer by the plasma of the etching gas in the processing container. According to the twenty-eighth aspect of the present invention, a plasma processing method is provided. The method includes: preparing at least a part of the surface to be -17- (13) 200401365

The operation of a component of Si, a first electrode, and a processing container of a second electrode at a position facing the first electrode; and the first electrode in the processing container is provided with an etching target layer and Covering the object layer to be etched to form an opening pattern of the object to be processed; work of introducing an inert gas into the processing container; work of applying high-frequency power to the first electrode; and work of the second electrode The operation of applying high-frequency power; the operation of introducing an etching gas in the aforementioned processing container; and, in the aforementioned processing container, by using the etching gas that is plasmatized by the aforementioned high-frequency power, it passes through the cover layer. The opening pattern is etched to the aforementioned etching target layer.

According to the twenty-ninth aspect of the present invention, there is provided a plasma processing method including: a sensor positioned in a processing container; placing a uranium-etched object layer and covering the etching object layer to form an opening pattern; and ArF photoresist or f2 photoresist layer composed of photoresist layer to be processed; the aforementioned processing container, the introduction of an etching gas containing Si compounds; the aforementioned etching gas to plasma ; And 'In the processing container, the plasma of the etching gas passes through the opening pattern of the photoresist layer, and the etching target layer is etched. [Embodiment] [Best Embodiment of the Invention] Hereinafter, an embodiment of the present invention will be described with reference to the attached drawings. -18- (14) (14) 200401365 Figure 1 is a cross-sectional view showing an example of a plasma processing apparatus that can implement the plasma processing method of the present invention. The plasma processing apparatus 1 includes a processing container 2. The processing container 2 is formed by metal, for example, aluminum whose surface is oxidized, and is grounded. A sensor 5 is provided on the bottom of the processing container 2 through the insulator 3 to function as an electrode at the lower portion of the parallel flat electrode. A high-pass filter (HPF) 6 is connected to the sensor 5, and a second high-frequency power source 50 is also connected through the integrator 51. An electrostatic chuck 11 is provided on the sensor 5, and a processing object W such as a semiconductor wafer is placed thereon. The electrostatic chuck 11 has a structure in which an electrode 12 is interposed between insulators, and a DC voltage is applied by a DC power source 13 connected to the electrode 12 in order to electrostatically adsorb the object to be processed W. Next, a focus ring 15 made of alumina, Si, or SiO 2 is arranged so as to surround the object to be processed W and improve the uniformity of etching. In addition, a shower head-shaped upper electrode plate 24 made of si, Si 02, amorphous carbon, or the like is provided above the sensor 5 and supported on a support 25 to face the sensor 5 . The upper electrode plate 24 and the supporting body 25 constitute the upper electrode 2 of the parallel plate electrode facing the sensor 5]. A low-pass filter 42 is connected to the upper electrode 21 ', and a first high-frequency power source 40 is also connected through the integrator 41. A gas introduction port 26 is provided at the center of the upper electrode 21, and a gas supply pipe 27 is connected to the gas introduction port 26. The gas supply pipe 27 is connected to the valve 2 sequentially from the gas introduction port 26 side. 8'mass flow controller 29 and process gas supply source 30. The predetermined processing gas is supplied from this processing gas supply source 30 -19- (15) (15) 200401365. 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, and the object to be processed W is transferred between the load lock chamber (not shown) adjacent thereto. In the device having such a configuration, first, the gate valve 32 is opened, and the object W is carried into the processing container 2 and placed on the electrostatic chuck η. After closing the gate valve 32 and depressurizing the processing container 2 by the exhaust device 35, the valve 28 is opened, and the etching gas supply source 30 is used to supply a predetermined processing gas to make the pressure in the processing container 2 In this state, high-frequency power is supplied from the second and second high-frequency power sources 40 and 50, and the processing gas is plasmatized, and the plasma treatment of the predetermined film of the object W is performed (electric resistance Slurry enhancement treatment or plasma engraving). In this state, before and after the high-frequency power is supplied from the first and second high-frequency power sources 40 and 50, a DC voltage is applied to the electrode in the electrostatic chuck] 2 to electrostatically adsorb the object W to be electrostatically charged. In this state, the chuck 11 is subjected to a predetermined plasma treatment. Fig. 2 is a sectional view showing another example of a plasma processing apparatus embodying the present invention. The plasma etching apparatus 61 includes a processing container 62. The processing vessel has a cylindrical shape with an upper portion 62a having a small diameter and a lower portion 62b having a large diameter, and is grounded by a metal such as aluminum whose surface is oxidized. A sensor 65 made of aluminum -20- (16) 200401365, which functions as the lower electrode of the parallel plate electrode, is provided at the bottom of the processing container 62 through an insulator. An electrostatic chuck 71 is provided on the sensor 65, and a to-be-processed object W such as a semiconductor wafer is placed on its top surface '. The electrostatic chuck 7 1 has a structure in which an electrode 72 is interposed between insulators. A DC power source 7 3 connected to the electrode 72 is applied to electrostatically adsorb the processing object W. Next, a focus ring 75 made of Si, SiO 2 or the like is arranged so as to surround the object to be processed W and improve the uniformity of etching.

In addition, above the sensor 65, a shower head-shaped upper electrode plate 81 made of Si or the like is provided, and is supported on the upper portion 62a of the processing container 62 to face the sensor 65. The processing container 62 also functions as a parallel plate-type electrode facing the sensor. A multi-pole ring magnet 82 is rotatably provided around the upper portion 62a of the processing container 62.

A gas inlet port 86 is provided in the center of the upper surface of the processing container 62. A gas supply pipe 87 is connected to the gas inlet port 86. The gas supply pipe 87 is connected to the valve 8 in sequence from the gas inlet port 86 side. 8. Mass flow controller 89 and process 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 to be processed W is transported between the load lock chamber (not shown) adjacent thereto. The first high-frequency power source 101 and the second high-frequency power source 102 are connected to the sensor 65 which is the lower electrode through the integrator] 0. The frequencies of the first and second high-frequency power sources 101, 102 are, for example, 100M Η z and 3.2 Μ Η z -21-(17) (17) 200401365 In the device thus constituted, first, The gate valve (not shown) is opened, and the object to be processed w is carried into the processing container 62 and is placed on the electrostatic chuck 71. Next, the gate valve is closed, and the pressure in the processing container 62 is reduced by the exhaust device 95. The valve 8 8 is opened, and a predetermined processing gas is supplied from the engraved gas supply source 90, so that the inside of the processing container 62 is supplied. The pressure becomes established. In this state, high-frequency power is supplied from the first and second high-frequency power sources ι01 and 102, plasma processing is performed on the processing gas, and plasma processing of a predetermined film of the object W is performed ( Resistance to plasma treatment (plasma etching). In this state, before and after the high-frequency power is supplied by the first and second high-frequency power sources 101 and 102, a DC voltage is applied to the electrode 72 in the electrostatic chuck 71, and the object to be processed W The static electricity is attracted to the electrostatic chuck 7 1, and in this state, a predetermined plasma treatment is performed. Next, an embodiment of the plasma processing method of the present invention will be described. (Embodiment Mode) Here, the plasma processing apparatus 1 shown in FIG. 1 is used to implement the Si 02 film 121 having the layer to be etched as shown in FIG. 3 and the film covering the 5 02 film 121 The photoresist layer [22], which is a mask layer composed of ArF photoresist or F2 * resist], is subjected to laser irradiation to improve the plasma resistance of photoresist layer 1 22; And after this operation, the photoresist layer 1 22 is used as a mask, and the plasma etching operation is performed on the etching target layer 1 2 1. -22- (18) (18) 200401365 As the A F photoresist or F 2 photoresist 'series, alicyclic acrylic resin, cycloolefin resin, cycloolefin-maleic anhydride resin, methyl Acrylic resin, etc. First, the "open gate valve 3 2" carries the object W into the processing container 2 "and is disposed on the electrostatic chuck 11. Next, the gate valve 32 is closed, and after the inside of the processing container 2 is depressurized by the exhaust device 35, the valve 2 8 ′ is supplied with a processing gas such as H2 from the processing gas supply source 30 to make the processing container 2 The internal pressure is a predetermined pressure, preferably 13.3 Pa (100 mTorr) or less, such as 6.67 Pa (50 mTorr). In this state, high-frequency power is applied to the upper electrode 21 and the sensor 5 serving as the lower electrode, plasma is applied to the processing gas, and a photoresist layer 122 in the object W is subjected to plasma. Irradiation. At this time, before and after the time when the upper and lower electrodes are used to supply high-frequency power, a DC power source 13 is applied to the electrodes 12 in the electrostatic chuck 1 1 to electrostatically adsorb the object W to the electrostatic chuck] 1. In order to replace the H2 plasma, therefore, you can irradiate: Plasma containing radon ;: Plasma with a processing gas of an inert gas such as He, Ne, Ar 'Kr, Xe or other plasma with other substances containing radon, including Plasma of substances and other substances, such as processing gases of inert gas. Examples of other substance systems having Η include NΗ3. Irradiation of these gases improves the plasma resistance of the photoresist layer 1 2 2 which becomes an organic layer. The detailed mechanism is not necessarily clear, but it is believed that the plasma system with fluorene promotes the crosslinking reaction of the photoresist layer that becomes an organic layer] 22, or by making the C-0 bond or C-fluorene bond become Strengthening chemical bonds for CC bonds' improves plasma resistance. In terms of ease of handling, it is preferable to use -23- (19) (19) 200401365 as the substance system having tritium as the aforementioned H2 or NH3. The NH3 system is also a substance having N, but as the process gas system, other substances having N, such as N2, may be used. The N2 system also has the advantage of being easy to handle. From the standpoint of improving the plasma resistance of the photoresist layer 1 22 by also using a substance having N, as the process gas system, a substance having N can be used instead of a substance having rhenium. The detailed mechanism for improving the plasma resistance in this state is not necessarily clear, but it is believed that the combination of N and C in the ArF photoresist forms a CN-based protective film on the surface of the ArF photoresist to increase the ArF light. Resistant to plasma resistance. In a state where the processing gas contains a substance having N such as N2, it is preferable to further include a substance having tritium. It is considered that the combination between N and C is promoted by the existence of Η. As a substance having tritium, one or more selected from tritium 2, CHF3, CH2F2, and CH3F can be used. ○ In this way, after the plasma is irradiated only for a predetermined time, the supply of processing gas and the application of high-frequency power are stopped. Then, the pressure in the processing container 2 is set to a predetermined pressure suitable for an etching operation, for example, 2.0 Pa (1.5 mTo: n ·), and the etching gas is supplied from a processing gas supply source 30. The etching gas system is preferably a gas containing fluorocarbon, for example, a gas containing C5F8. Specific examples include C5F8 + 02 + Ar. The etching target portion is a Si02 layer. When the etching gas contains C5F8, the selection ratio of the Si02 film m serving as the etching target portion to the photoresist layer 1 2 2 serving as the organic layer (the uranium etching speed of the etching target portion). / Etch rate of the organic layer) becomes higher. Even in C5F8, it is better to choose a higher linear c5F8, even if it is among them, especially -24- (20) (20) 200401365 when using 1 '1' 1, 4, 4, 5 In the state of 5,5 -octafluoro-2 -pentyne (hereinafter referred to as p 2 -CSF8 ".), The aforementioned selection ratio becomes extremely large. In addition, as the etching gas system, C4F6 is also suitable. By using C4F6 in the etching operation, the polymer is deposited on the ArF photoresist. Therefore, the reduction of the photoresist's pores does not occur, and the etched holes can be formed while maintaining the required opening shape. In this way, an etching gas flows, and high-frequency power is applied to the upper electrode 21 and the sensor 5 serving as a lower electrode. The etching gas is plasmatized, and the plasma is used as a photoresist layer. 12 is used as a mask, and the Si02 film 121 is etched. In the etching, an end point detector (not shown) detects a predetermined luminous intensity, and the etching is terminated based on this. In addition, the etching target system is not limited to the Si02 film, and can also be applied to oxide films (oxygen such as TEOS, BPSG, PSG, SOG 'thermal oxide film, HTO, FSG, organic silicon oxide film' CORAL (Novel as)). Compounds) or low dielectric organic insulating films. In this state, it is possible to use, as the etching gas, a gas in which another gas is added only to the processing gas depending on the material of the etching target portion. If the plasma can be irradiated with the processing gas and the etching is performed only by adding another gas, the plasma discharge can be maintained and continuously performed: the plasma irradiated with the processing gas and the etching operation. As a specific example, it is implemented in series: the operation of plasma irradiating the processing gas' uses H2 as a processing gas, and then uses a mixed gas of H2, CF4, and Ar as an etching gas, and etches, for example, an organic oxide film as an etching target portion -25- (21) 200401365 assignment. In addition, 'it is not limited to photoresist materials with low plasma resistance of ArF or F2 photoresist'. In order to replace these, it may also be other organic photoresist layers, not even limited to photoresist. It may be another organic layer. The structure of the plasma processing apparatus is not limited to that shown in FIG. 2. Next, an example of the method of the first embodiment will be described.

Here, as various conditions for the operation of plasma irradiation, the pressure in the processing vessel is 6.7 Pa (50 mTorr), the flow rate of the processing gas H2 is 0.05 to 0.2 L / min (50 to 200 sccm), and the irradiation time is 30 In the second 'the high-frequency power of 60 MHz is applied to the upper electrode at a power of 500 to 1000 W', the high-frequency power is not applied to the lower electrode. In addition, as conditions for the etching operation, the pressure in the processing vessel is set to 2_0Pa (15mT0rr), and the flow rates of the etching gases C5Fs, Ar, and 02 are 0.015L / min (15sccm) and 0.38L / min (380sccm) 〇.〇I9L / min (19sccm), the high-frequency power of 60MHz frequency is applied to the upper electrode with 2170W power, and the high-frequency power of 2MHz frequency is applied to the lower electrode with 1550W power. In this embodiment and the comparative example in which the plasma irradiation operation is omitted, the selection ratio of the Si02 film to the ArF photoresist mask during the etching operation (the etching speed of the Si02 film / the ArF photoresist mask Etch rate). For all four measurement sites of the object to be treated W, as in the example, the plasma selective irradiation was performed to increase the selection ratio as compared to the comparative example in which the plasma irradiation was not performed. The increase rate is 6 ~ 19%. -26- (22) 200401365 (second embodiment)

Here, using the aforementioned plasma etching apparatus, the following is implemented: for the S i Ο 2 film 1 3 1 shown in FIG. 4A, the anti-reflection film 132 covering the S i Ο 2 film 1 3 1 and covering the reflection prevention Film] 32 and the object to be processed W 3 of the photoresist layer I 3 3 composed of an ArF photoresist or F2 photoresist passes through the opening pattern of the photoresist layer 1 3 3 to etch the antireflection film 1 3 2 At the same time, the first etching operation to improve the plasma resistance of the photoresist layer 1 3 3 (Fig. 4 A); and after this operation, the photoresist layer 133 is passed to the Si0 2 film. The second etching operation of plasma etching is performed (FIG. 4B).

First, the object to be processed W is placed in the processing container 2 and a processing gas supply source 30 is used to supply a processing gas, such as N2 and H2, which also serves as the first etching gas. At the same time, the pressure in the processing container 2 is set to a predetermined level.値, for example] 07Pa (8000mTorr). The pressure in the processing container at this time is preferably 107 to 160 Pa (800 to 1200 mTorr). Since the photoresist layer 1 3 3, especially the shoulders of the opening pattern is also etched when it is lower than 10 7 P a, the opening pattern is not etched when the opening pattern is larger than 16 0 P a. Sake = As a processing gas that also has the first etching gas, a gas containing N, such as N2 'NHs' in addition', or a gas containing tritium, for example, selected from H2, CHF3, CH2F2, and CH3F can be used. 1 or more. Next, the upper and lower electrodes "apply high-frequency power" to plasmatize the first etching gas ", and the antireflection film 1 3 2 is etched with the photoresist layer 1 3 3 as a mask. As the anti-reflection film 'system, amorphous carbon or -27- (23) 200401365 organic polymer material can be used. This etching system also has a treatment for improving the plasma resistance of the photoresist layer 1 3 3. When the etching is performed only for a predetermined time, the first saturation is completed.

The process gas and the etching gas can be made the same in this way, without the need to switch the gas between the photoresist layer 1 3 3 to irradiate the plasma and the operation to etch the antireflection film 1 3 2 for short The treatment of time can achieve the improvement of production efficiency. In addition, during the etching of the anti-reflection layer 1 2 3, 'the plasma resistance improvement treatment of the ArF photoresist can be performed', and therefore, this extra device or space is not required. Next, the process gas (the first etching gas) is switched to the etching gas (the second etching gas), which is the same as the first uranium etching gas, and is performed with the photoresist 1 3 3 and the SiO 2 film 1 31. The second etching of plasma etching. The etching gas system at this time is the same as that of the first embodiment, and preferably contains fluorocarbon, for example, C5F8. Specific examples include C5F8 + 02 + C0 + Ar. Even in C5F8, linear C5F8 is preferred,

Especially 2-C5Fs. C4F6 is also suitable as the fluorocarbon system used as the etching gas. In addition, even in this second embodiment, the etching target system is not limited to the Si02 film, but can be applied to TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic silicon oxide film, CORAL (Novel as company) and other oxide films (oxygen compounds) or low dielectric organic insulating films. In addition, the photoresist material having a low plasma resistance is not limited to the ArF photoresist or the F2 photoresist, and may be other organic photoresist layers, not even the photoresist, and other organic layers. Plasma -28- (24) 200401365 The structure of the processing device is not limited to the one shown in Figure 1. Next, an example of the method of the second embodiment will be described.

Here, as various conditions of the first etching, the pressure in the processing vessel is 107 Pa (800 mT0rr), and the flow rates of the processing gas (first uranium etching gas) N2 and plutonium 2 are 0.6 L / mi η (6 0 0 sccm), applying high frequency power of 60 MHz to the upper electrode with 100 W power, and applying high frequency power of 2 MHz to the lower electrode with 300 W power. Various conditions for the second etching are such that the etching gas contains 1,2,3,3,4,4,5,5-5-octafluoromonocyclo-1-pentyne (hereinafter, described as "c-C5FS".) The state of the gas (Example 2-1), the pressure in the processing vessel was 2.0 Pa (15mTorr), and the flow rates of the uranium-engraved gases c—C5F8, Ar, and 02 were 0.015 L / min (15 sccm) and 0.38 L / min, respectively. (380sccm), 0.019L / min (19sccm), at a frequency of 60MHz,

High-frequency power is applied to the upper electrode at a power of 21 70W, and high-frequency power is applied to the lower electrode at a frequency of 2MHz 'power at 1550W; when the etching gas is in a state containing 2-C5F8 (Example 2-2), the processing container Internal pressure becomes 2.7Pa (20mTorr), etching gas 2 — C ;; F8, Ar, 〇2 'CO flow rate is 0.027L / min (27sccm), 0_5L / min (SOOsccm), 0.027LX min (2 7 sccm) ), 0.05L / min (50sccm), applying high-frequency power to the upper electrode at a frequency of 60MHz and a power of 1,600W, and applying high-frequency power to the lower electrode at a frequency of 2MHz and a power of 2000W. On the other hand, after performing c F 4 by considering that the treatment gas does not have the resistance of ArF photoresist -29- (25) 200401365 to improve the plasma property, the [] f worm will be the same as the M example. 2-1, and the second ΙΜ is performed by using a gas containing c—CsFg. As Comparative Example 2-1, it is the same as that in Example 2-1 and the second is performed by using a gas containing 2—C 5 F 8 Etcher 'is used as Comparative Example 2-2. The results are shown in Table 1. Table 1 Etching speed of Si02 / Ar photoresist for processing gas etching gas in the second etching operation Example 2 -1 n2 + h2 C-QF8 gas-containing 8.3 Comparative Example 2 -1 cf4 C-C 5 F 8 gas 6.3 Example 2-2 n2 + h2 containing 2-C5F8 gas Λ Λ 0 J. J Comparative Example 2-2 cf4 containing 2-C 5 F 8 gas 2 2.5

As shown in Table 1, it was confirmed that in the first etching operation of the anti-reflection film, the plasma resistance of the ArF photoresist film was improved by using a plasma of a mixed gas of N2 + Η2, and SiO2 after the etching In the second etching operation of the film, the selection ratio of the Si O 2 film to the Ar F photoresist film (etching speed of Si 02 / etching speed of ArF photoresist) becomes higher. (Third Embodiment) Here, the plasma etching apparatus 61 'shown in FIG. 2 is used to implement: For the Si02 film having a layer to be etched as shown in FIG. 5A] 41, -30- (26) (26) 200401365 Antireflection film 142 covering the Si02 film 141 and a photoresist layer covering the antireflection film 1 42 and composed of an ArF photoresist or an Fs photoresist] 43 to be processed W ' Plasma improves the plasma resistance of the photoresist layer M3, and at the same time, through the opening pattern 1 4 3 a of the photoresist layer 1 4 3 a, the operation of engraving the anti-reflection film 1 42 is performed (Figure 5 A) ); And, after this operation, plasma uranium engraving is performed on the Si02 film 141 through the photoresist layer 143 (FIG. 5B). Even in this embodiment, an alicyclic acrylic resin, a cycloolefin resin, or a cycloolefin-maleic anhydride resin can be used as the ArF photoresist or ρ2 photoresist 'system. As the anti-reflection layer, an organic polymer material or amorphous carbon can be used. First, a gate valve (not shown) is opened, and the object to be processed W is carried into the processing container 62, and the electrostatic chuck 71 is arranged. Next, the gate valve is closed, and after the pressure in the processing container 62 is reduced by the exhaust device 95, the valve 8 8 is supplied with a processing gas from a processing gas supply source 90, for example, Η: The pressure becomes established. The process gas may be only Η2 ', or a diluent gas such as Ar having the same flow rate as η 2 may be added. As the processing gas, it is possible to use other substances having rhenium instead of h2. In this state, 'the high-frequency power is supplied from the first and second high-frequency power sources 101'102' is plasma-treated with respect to the processing gas, and acts on the object W to be processed. At this time ', before and after the high-frequency power is supplied, a DC power source 73 is applied to the electrode 72 in the electrostatic chuck 71 to electrostatically adsorb the object to be processed w on the electrostatic chuck 71. -31-(27) (27) 200401365 As described above, 'the plasma treatment is performed at a predetermined time to improve the plasma resistance of the photoresist layer 1 4 3' and the antireflection layer is etched 4 2 but 'at this time The pressure in the processing vessel 62 is preferably 1 3 · 3 Pa (100 mTorr) or less. In this manner, when the plasma having a low-pressure treatment gas containing η is irradiated onto the photoresist layer 143 as the cover layer, the plasma resistance of the modified cover layer is improved. By increasing the plasma resistance of the photoresist layer 1 4 3 and by opening the opening pattern 1 4 3 a of the photoresist layer 1 4 3 a later, when performing plasma etching on the etching target layer, the etching target layer can be improved. The selection ratio for the mask layer, that is, the etching speed of the etching target layer / the etching speed of the mask layer. In addition, in this etching operation, it is possible to prevent streaks or grooves from entering the photoresist layer 1 4 3 serving as a mask layer due to the plasma. In addition, it is possible to suppress the opening of the photoresist layer 1 4 3 serving as the cover layer from expanding. The detailed mechanism for improving the plasma resistance of the photoresist layer 1 4 3 serving as the cover layer is not necessarily clear, but it is considered that the photoresist layer is caused by the action of the samarium radicals on the surface layer of the photoresist layer 143. The gas such as CH4 is extracted from the inside, so that the chemical bond between the carbon in the cover layer is changed to become stronger. In addition, it is preferable that the processing gas does not contain a substance having N. When a substance containing N is contained in the processing gas, a protective film system containing C and N as the main component covers the side wall surface of the cover layer. It is believed that the tritium radical system having the effect of improving the plasma resistance cannot start from the side wall surface. The penetration to the inside cannot exceed the thick width of the plasma resistance of the side wall surface of the cover. From the viewpoint of further alleviating the damage to the photoresist layer 1 4 3 during processing, the processing pressure is preferably 8 to 3 OmTorr. -32- (28) (28) 200401365 In addition, by supplying high-frequency power for plasma formation to the sensor 65 from the first high-frequency power source 101, the photoresist layer that becomes the cover layer is improved. 1 43 resistance to plasma. The frequency at this time is preferably 100 MHz or more. In addition, the sensor 65 and the second high-frequency power source 102 can be used to apply other high-frequency power different from the above-mentioned one, preferably one with a frequency of 3 MHz or more, to suppress activated species in the plasma. , Especially ions. The other high-frequency power system is preferably 1000 W or less. Since it can be processed under an atmosphere of low voltage and low power (low bias voltage), the damage to the photoresist layer 143 which becomes the cover layer is minimized. In addition, in a low-pressure, low-power (low-bias) atmosphere, 'Η radicals start from the side walls of the photoresist layer 1 4 3 and penetrate into the interior. Therefore, the photoresist layer 1 4 3 can be reached. The plasma resistance of the side wall starts to the thick part of the interior. Since the photoresist layer 143 is an organic material and contains carbon, as a result, such a surface modification effect becomes remarkable. In addition, as for the ArF photoresist or F2 photoresist constituting the photoresist layer 143, the plasma resistance is considerably changed before and after the plasma resistance improvement treatment. Therefore, this type is suitable for microfabrication. On the occasion of the treatment, the great effect was obtained. In addition, at the same time as the improvement of the plasma resistance, the anti-reflection layer 1 4 2 necessary for the etching of the target layer is etched. Therefore, the photoresist layer 1 43 that becomes the mask layer can be etched and etched. Anti-reflection layer 1 42. At this time, as described above, by supplying high-frequency power at a frequency of 100 MHz or more to the sensor 65, the H2 in the dissociation processing container 62 becomes various activated species. Among the activated species, the tritium radicals mainly cause The plasma resistance of the photoresist layer 143, which becomes the cover layer, is improved. Η radical -33- (29) 200401365 and the ion system mainly cause the etching of the reflection prevention layer 1 42. These active species have a good balance system. Therefore, it is possible to improve the plasma resistance of the photoresist layer 1 43 as the cover layer, and at the same time, effectively etch the anti-reflection layer 42. In addition, the ionic action in the activated species can be controlled by supplying high-frequency power to the sensor 65 from the second high-frequency power source 102 and a high-frequency power source having a frequency of 3 MHz or more.

Next, the aforementioned processing gas, that is, an etching gas for etching the Si02 film 141 to be an etching target layer, such as a fluorocarbon gas containing a mixed gas of C4F6, 02, and Ar, is supplied by the first and second high-frequency power sources. A high-frequency power is applied to the sensor 65, and the aforementioned processing gas is plasmatized. With the plasma, the photoresist layer 1 4 3 is used as a mask to etch the Si02 film 141. In the etching, an end point detector (not shown) can be used to detect a predetermined luminous intensity, and the etching can be terminated based on this.

In addition, even in this embodiment, the etching target system is not limited to the Si02 film, but it can also be applied to TEOS, BPSG, PSG, SOG 'thermal oxide film, HTO, FSG, organic Si oxide film, CORAL (Novel as a company) ) And other oxide films (oxygen compounds) or low dielectric organic insulating films. In addition, the photoresist material with low plasma resistance is not limited to ArF photoresist or F2 photoresist, and may be other organic photoresist layers, not even limited to photoresist, or other cover layers. . The structure of the plasma processing apparatus is not limited to that shown in FIG. Next, an example based on this embodiment will be described. Here, first, the pressure in the processing chamber was set to three types: 1.07Pa (-34- (30) 200401365 8 OmTorr), 40Pa (30mTorr), and 13.8 Pa (100mTorr). Source to supply as a source of processing gas :. The frequencies of the first and second high-frequency power sources are 100MHz and 3.2MHz, respectively, and their powers are 240OW and 500W. In addition, the evaluation was performed even in a state where power was not supplied by the second high-frequency power source (= 0W). The evaluation was performed by observing the cross-sectional state of the mask layer with a microscope (SEM (scanning electron microscope)). As a result, when the pressure was 1.07Pa (80mTorr) or 400Pa (30mTorr), there was almost no entry of stripes into the cover layer, entry of grooves, or expansion of the openings. When the pressure becomes 1 33Pa (] OOmTorr), there is not much entry for the streaks or grooves of the cover layer or expansion of the openings. When the pressure becomes high, streak entry and groove entry are likely to occur.

In addition, the electric power supplied by the second high-frequency power supply also reduces the number of streaks and grooves or openings of the cover layer at 0W compared with 500W. . Taking these results into consideration, it is preferable that the power system supplied from the second high-frequency power source is Γ0 0 W or less. In addition, when the pressure was fixed at 1.07Pa (80mTorr) and the H2 flow rate was changed to 50 mL / min (seek), 100 mL / min (seek), 120 mL / min (sccm), and 200 mL / min (sccm), When the flow rate is reduced, the streak entry and groove entry or the opening of the mask layer are enlarged, and the number of openings is reduced. In the following, the etching process is performed on the Si 102 film which is the object layer to be etched. In the processing container, a mixed gas of C4F6, 〇2, and Ar -35- (31) (31) 200401365 is used as an etching gas so that The pressure inside the processing vessel becomes 666Pa (SOmTorr), and the high-frequency power supply to the sensor 5 comes from the first! The high-frequency power source is 600W, and the second high-frequency power source is 800W. The worm-etched gas is plasmatized by the supply of local frequency power from the first frequency power source, and the Si02 film is etched to become an etching target layer. After the end of the etching by the end point detection method or the like, the SEM observation was performed in the same manner. As a result, even after the plasma etching of the etching target layer was completed, the mask layer was not significantly reduced. Stripe entry • Groove entry or the opening of the cover layer is enlarged. From this, it is known that the improvement effect of the plasma resistance of the cover layer caused by the present invention is also continued after the plasma etching of the etching target layer. (Fourth Embodiment) Here, using the plasma processing apparatus 1 shown in FIG. 1 described above, it is performed to cover the Si Si layer 1 5 1 having an etching target layer shown in FIG. 6A and cover the Si The anti-reflection layer 152 of the 02 layer 151 and the photoresist layer 1 5 3 which is a mask layer forming an opening pattern 153 a covering the anti-reflection layer 152 and composed of an ArF photoresist or an F2 photoresist W 'Plasma etching through the opening pattern of the photoresist layer 1 5 3' for the antireflection film 16 2; and 'work of etching the Si 102 layer 1 51'. Even in this embodiment, as the ArF photoresist and the F2 photoresist, an alicyclic acrylic resin, a cycloolefin resin, a cycloolefin-maleic anhydride resin can be used. As the anti-reflection layer, an organic polymer material or amorphous carbon can be used. -36- (32) (32) 200401365 In this embodiment, the first etching operation for plasma etching is performed on the antireflection film 1 5 2 through the opening pattern 1 5 3 a of the photoresist layer 1 5 3, The Si02 layer is etched by the opening pattern of the photoresist layer 1 53] 5 1 The second etching operation up to the middle and the third etching operation that also etches the Si 02 layer 1 5 1 after the second etching operation 3 stages' to perform such an etching operation. The second etching operation among these operations becomes S !. [Layer]] The initial etching operation is performed at 5], and the third etching operation is performed as the main etching operation of the Si 02 layer 151. First, the gate valve 32 is opened, and the object to be processed W 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 reduced by the exhaust device 35, the valve 28 is opened, and the etching gas supply source 30 is used to supply H2 so that the pressure in the processing container 2 is increased. Become established. In this state, the "second high-frequency power source 40" 50 is used to supply high-frequency power ", and the plasma is converted to H2 gas, which acts on the object w" through the opening of the photoresist layer I 5 3 The pattern is etched for the anti-reflection layer 152 (first etching; FIG. 6A). On the other hand, before and after the time when the first and second radio frequency power sources 40 and 50 are used to supply high-frequency power, the electrode 12 in the electrostatic chuck n is applied with a DC power source 13 to electrostatically adsorb the subject W. On the electrostatic chuck]]. In the etching, a predetermined luminous intensity is detected by an end point detector (not shown), and the supply of high-frequency power is stopped based on this, and the first etching operation is ended. Next, in the same processing container or other processing container, the same etching operation as in the first etching operation is performed, and a mixed gas of CF 4 and H 2 is supplied, and the S 〇 2 layer I is etched through the opening pattern of the photoresist layer 153. 5 1 —Until on the way (33) (33) 200401365 (second etching operation; Figure 6B). If a predetermined etching time elapses, for example, 60 seconds, the second etching operation is terminated. Then, in the same processing container or other processing container, the same as the second etching operation, a gas different from the second etching operation, such as a mixed gas of linear C 5 F s, 〇2, and Ar, and Si02 is also etched. Layer I 5 1 (3rd etching operation: FIG. 6C). This third etching operation is terminated based on the end point detection. In this way, the second etching operation of the Si02 layer 1 5 1 using the plasma of CF4 and H2 can be performed on the surface of the ArF photoresist layer 1 5 3 which becomes the mask layer, especially the Si02 layer 1 5 Many protective films are formed near the boundary between the first and second layers, which can suppress the deformation of the shape of the photoresist layer 153 in the third etching operation later. In addition, the anti-reflection layer 15 2 can be etched by using the plasma of plutonium 2 in the first uranium etching operation, and the shape deformation of the photoresist layer 15 3 in the third etching operation can be more effectively suppressed. It is considered that this is because the plasma near the surface of the photoresist layer 153 serving as the cover layer is separated from oxygen atoms by the plasma of Η2, and a strong carbon-carbon bond is formed by the structure. The effect of deforming the shape of the photoresist layer [53] is that the material becomes a methacrylic resin (referred to as a resin in which methacrylic acid is put into the structure) which is particularly easily deformed by the plasma. In the state, it becomes remarkable. However, the same effect can be obtained even with other resins such as acrylic resin (referred to as a resin in which acrylic is incorporated in the structure). However, in a state where the material of the photoresist layer is an acrylic resin, among the finely-processable mask materials, the resistance to deformation of the plasma is relatively large. Therefore, in the first etching of the antireflection layer, No-38- (34) (34) 200401365 — Ha gas must be used. You can also use CF4 plasma, which has an etching rate higher than H2 and has the least damage to the cover layer even in fluorocarbon, at high speed. Here, the anti-reflection layer 15 is etched. In addition, as the etching gas for the third etching operation, a gas including linear C5F8 and 〇2 can be used to make the S i Ο 2 layer 1 5 1 which is an object to be etched more exotic and faster. Etching. In addition, the etching gas system of the third etching operation is not limited to this, but it is preferably another gas different from the mixed gas of CF4 and H2 used in the second etching operation. This is because after the second etching operation to form a structure that suppresses the deformation of the shape of the mask layer, it can be switched to an etching gas for the third etching operation, and has, for example, more exotic etching or higher-speed uranium etching. The reason for the required function. From the viewpoint of etching the Si 0 2 layer 1 5 1 more quickly, a fluorocarbon-containing gas can be suitably used as the etching gas system. However, it is particularly preferable that the foregoing includes a linear C 5 F 8 And gas of 〇2 = above, the etching operation in the state where the antireflection layer 1 52 is present will be described, but in the state where the antireflection layer is not present, the aforementioned first etching operation can be omitted. First, it can be implemented: CF4 and h2 are plasma-etched, and the Si02 layer, which is the etching target layer, is etched through the opening pattern of the ArF photoresist layer until the middle of the etching process. After this initial etching operation, perform · 'For the main etching operation, it is preferable that the etching gas containing fluorocarbon, and more preferably the aforementioned gas containing the linear c5F8 and 02, be plasma-etched to etch the remaining portion of the Si02 layer that becomes the etching target layer. In this state, it also becomes the cover layer -39-(35) (35) 200401365

The surface of the ArF photoresist layer is formed with a large number of protective films near the boundary between the Si 02 layers that are to be etched layers, which can suppress the shape deformation of the ArF photoresist layer in the main etching operation thereafter. In addition, even in this embodiment, the etching target system is not limited to the SiO 2 film, but can be applied to TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic Si oxide film, CORAL (

Novelas) and other oxide films (oxygen compounds) or low-dielectric organic insulating films. In addition, 'the photoresist material having a low plasma resistance is not limited to the Ar F photoresist or F 2 photoresist', and may be other organic photoresist layers, and it is not even limited to photoresist. Cover curtain layer. The structure of the plasma processing apparatus is not limited to that shown in the first figure. Next, an example based on this embodiment will be described. Regarding the anti-reflection layer 152 of the object to be processed shown in FIG. 6A and the Si 02 layer 151 as the object to be etched, the apparatus shown in FIG. 1 was used to perform No. 1 ~ under the conditions shown in Table 2. Etching of 6. In addition, even if etching is performed on any one, the frequency of the first high-frequency power source is 60 MHz, and the frequency of the second high-frequency power source is 2 MHz. Specifically, N ο · 1 to 3 are made of Ar F photoresist of acrylic resin as the photoresist layer 1 5 3 'Each of the third etching operations uses C 4 F 6' Ο 2 and A r Among them, NO. 1 is used in the first etching operation, using CF4, and no second etching operation is performed; No. 2 is used in the first etching operation, using CF4, and CF2 and H2 are used in the second etching operation; No. 3 is used in the first etching operation, and CF2 and H2 are used in the second etching operation. In addition, No. 4 to 6 uses ArF photoresist -40- (36) (36) 200401365 as the photoresist layer 1 5 3, and any of the third etching operations uses straight Chains c 5 F 8, 〇2, and Ar. Among these, 'N 〇. 4 is used in the first etching operation, and CF4 is used, and the second etching operation is not performed; No. 5 is used in the first etching operation, and CF 4 is used. 'In the second etching operation, CF 4 and Η 2 were used; N 0.6 was used in the first etching operation, using Η 2, and in the second etching operation, CF 4 and H 2 were used. After the completion of all operations, the shape deformation of the photoresist layer 153 was investigated for samples of each condition. As a result, in Nos. 1 to 3 where an acrylic resin was used as the photoresist layer 153, No. 1 in which the second etching operation was performed did not have a vertical stripe that was an indicator of the deformation of the photoresist layer. No. 2 and 3 of 2 etching operation, whether or not the gas used in the first etching operation, there are vertical stripes. On the other hand, in Nos. 4 to 6 using a methacrylic resin having a lower plasma resistance than an acrylic resin as the ArF photoresist layer 1 5 3, there is no No. · 4 system for performing the second etching operation. Vertical stripes. In addition, it was confirmed that in the first etching operation, the No. 5 series of vertical streaks performed in the second etching operation using C F4 was reduced, and thereby the vertical etching was suppressed by the second etching operation. When the second etching operation was performed and the gas in the first etching operation was changed to N 0.6 of H2, there were no vertical stripes. That is, it was confirmed that, in a state where the photoresist layer 1 5 3 is made of a material having low resistance to plasma, in addition to the second etching operation, the first etching operation is also performed by using Η 2, The anti-reflection layer] 5 2 ′ does not cause a vertical streak that is an index of deformation of the photoresist layer. -41-(37) 200401365

No. 1 2 3 4 5 6 ArF Photoresist Acrylic Resin Methacrylic Resin No. 1 Etching Operation Pressure (Pa) (Number in parentheses is m T 〇rr) 6.7 (50) 2.0 (15) 6.7 (50) 2.0 (] 5) Power from the first high-frequency power supply (W) 1000 2200 1000 2200 Power from the second high-frequency power supply (W) 100 1 00 100 100 Gas and flow rate (mL / min) CF4: 1 〇〇H2 : 1 00 CF4: 100 H2: 100 The second etching operation pressure (Pa) (the number in parentheses is mTorr) M 2.7 (20) ite 2.7 (20) Power from the first high-frequency power source (W) 1800 1800 from 2 Power of high frequency power (W) 1 800 1800 Heating body and flow rate (mL / min) CF4: 120 H ,: 1 80 CF4: 1 20 H2: 1 80 Third etching operation pressure (Pa) (number in parentheses) MTorr) 6.7 (50) 2.7 (20) Power from the first high-frequency power supply (W) 1800 1 800 Power from the second high-frequency power supply (W) 1150 1800 Gas and flow rate (mL / min) C4F6: 25 〇 2:26 Ar: 700 straight chain c5f 〇2: 3 A r: 5 (,: 27 0) 0 vertical stripes are dirty ^ 1 \\ ftE > 1 \\ have younger sister / «-42-(38) 200401365 (Fifth Embodiment)

Here, the plasma processing apparatus 1 shown in FIG. 1 is used to implement an etching target layer having a Si02 layer and the like formed on a substrate layer 160 such as Si shown in FIG. 7A. 161 (thickness example: 1500 nm), an organic reflection prevention layer 162 (thickness example: 60 nm) covering the etching target layer 161, and an opening pattern 163a (diameter example: 0 · 1 8 // m) covering the organic reflection prevention layer 162 ) And the object W of the photoresist layer 1 63 composed of an ArF photoresist or an F2 photoresist is passed through the opening pattern 1 63 a of the photoresist layer 1 63 to the organic reflection prevention layer 1 62 Plasma etching; and then, plasma etching is performed on the uranium-etched target layer 161 to form an opening pattern 161a. Hereinafter, description will be made with reference to the flowcharts in FIGS. 7A to 7C and FIG. 8.

As the ArF photoresist or F2 photoresist constituting the photoresist layer 163, an alicyclic acrylic resin, a cycloolefin resin, a cycloolefin-maleic anhydride resin, and a methacrylic resin can be used. As the organic antireflection layer 162, an organic polymer material can be applied. In addition, in this embodiment, the upper electrode plate 24 of the plasma processing apparatus 1 is made of a material containing at least Si on the surface of Si, Sic and the like. First, the gate valve 32 is opened, and the object to be processed W is carried into the processing container 2 (step), and is placed on the electrostatic chuck 11. Next, the gate valve -43- (39) (39) 200401365 3 2 is closed, and the pressure in the processing container 2 is reduced by the exhaust device 35. Then, the valve 28 is opened, and the processing gas supply source 30 is provided. The H2 gas is supplied (step 2) so that the pressure in the processing container 2 becomes a predetermined pressure. In this state, high-frequency power is supplied from the first high-frequency power source 40 and the second high-frequency power source 50, and plasma is generated for H2 gas. The anti-reflection layer 16 is etched (step 3) (FIG. 7A). On the other hand, before and after the high-frequency power is supplied by the first high-frequency power supply 40 and the second high-frequency power supply 50, a DC voltage is applied to the electrode 12 in the electrostatic chuck 11 to electrostatically adsorb the object W to be treated. Electrostatic chucks 1 on 1. If the etching is performed only within a predetermined time, the supply of high-frequency power or etching gas is stopped, and the etching of the organic reflection preventing layer 162 is finished (Fig. 7B). An end point detector (not shown) can be used to detect the luminous intensity of a specific substance in the plasma, and the etching operation can be terminated based on this. In the state of this embodiment, during the etching of the organic reflection preventing layer 162 caused by the H2 plasma, Si and H2 plasma are supplied from the upper electrode plate 24 composed of at least the surface of Si. , Acting on the surface of the photoresist layer 163, and on the surface of the photoresist layer 163, a thin protective layer 163b containing Si—O or Si—C is formed. In other words, it is thought that during the etching process of the organic reflection prevention layer 1 62 caused by the H2 plasma, a reaction with C or hafnium on the surface of the photoresist layer 16 3 occurs, and as a result, it becomes reactive. A state where most of the high C or 0 exists on the surface of the photoresist layer 16 3, and these highly reactive c or 0 react with S i supplied from the upper electrode plate 24 to form S i- -44-(40) 200401365 Thin protective layer 163b of C or Si — 0 and other substances. In this way, a thin protective layer 1 6 3 b is formed on the surface of the photoresist layer 1 6 3 when plasma etching is performed on the organic reflection prevention layer 1 6 2 through the opening pattern 163a of the photoresist layer 163. There is no need for any extra work. It can improve the electrical resistance of the photoresist layer 163. Therefore, when the organic reflection preventing layer 162 is etched, no surface cracks or streaks are generated, and the plasma resistance of the photoresist layer 163 can be maintained at a high level.

Then, 'in the same processing container or other processing containers, as the etching gas system, for example, C 5 F 8, 0 2 and A r are supplied (step 4), and passed in the same order as that of the organic reflection prevention layer 1 62. The opening pattern 16 3 a of the photoresist layer 16 3 is subjected to plasma etching on the etching target layer 16 1 (step 5). Thereby, for example, an opening pattern 1 6 1 a with a high aspect ratio is formed on the etching target layer 1 6 (FIG. 7C). Next, after the etching of the etching target layer 161 is completed, the object w to be processed is taken out of the processing container 2 through the gate valve 32 (step 6).

In the etching of the etching target layer 161, in the state of this embodiment, 'the protective layer 163b is formed on the surface of the photoresist layer 163, and the state is in a state of high plasma resistance. Therefore, even if It is plasma etching in the etching target layer 1 61, and also maintains the plasma resistance of the photoresist layer 63 or the selection ratio of the etching target layer 16 1 to the photoresist layer 16 3 to a high degree. Therefore, the surface of the photoresist layer 163 does not cause wrinkles or vertical streaks, and plasma etching can be performed on the etching target layer 161 under the condition of a high etching rate. As a result, no extra work is required, and at the same time, the production efficiency in plasma etching is improved. In addition, no openings in the photoresist layer 1 63 * 45-(41) (41) 200401365 pattern 163a occurred. Therefore, the photoresist layer 163 was used as a mask to form the target layer I. The accuracy of the opening pattern 1 6 1 a on 6 1 is also improved. From the viewpoint of improving the plasma resistance of the photoresist layer 163 in the aforementioned step 2, in order to replace Η2, He or N2 may be used. However, in the state where He and N2 are used, the organic antireflection layer 1 62 is hardly etched. In addition, there may be no organic reflection prevention layer] 62. At this time, the plasma resistance of the photoresist layer 163 may be specifically improved by at least one plasma treatment of H2, He, and N2. Next, a modification of this embodiment will be described with reference to the flowcharts of FIGS. 9A to 9C and FIG. 10. In this modification, it is shown that after the organic antireflection layer 16 is etched by a plasma of CF4 gas, the plasma is caused by the plasma of H2 gas before the etching of the target layer 16 is performed. An example in which a protective layer 16 3 b is formed on the surface of the photoresist layer 16 3 by processing. That is, first, the gate valve 32 is opened, the object to be processed W is carried into the processing container 2 (step), and it is placed on the electrostatic chuck 11. Next, the gate valve 32 is closed, and the inside of the processing container 2 is depressurized by the exhaust device 35. Then, the valve 28 is opened, and CF4 gas is supplied from the processing gas supply source 30 (step 12), so that the processing is performed. The pressure inside the container 2 becomes a predetermined pressure. In this state, high-frequency power is supplied from the first high-frequency power source 40 and the second high-frequency power source 50. The plasma of CF4 gas is passed through the opening pattern of the photoresist layer 163. Prevent layer 162 to etch -46- (42) 200401365 (step 13) (Figure 9A). On the other hand, before and after the high-frequency power is supplied by the first high-frequency power source 40 and the second high-frequency power source 50, a DC voltage is applied to the electrode 12 in the electrostatic chuck 11 to electrostatically adsorb the object W to be treated. The electrostatic chuck 1 1 is on. If the etching is performed only within a predetermined time, the supply of high-frequency power or etching gas is stopped, and the etching of the organic reflection preventing layer 162 is terminated. An end point detector (not shown) can be used to detect the luminous intensity of a specific substance in the electric prize, and the etching operation can be terminated based on this.

Then, the gas supplied to the processing container 2 is switched to H2 gas (step 14), and the H2 gas is plasmatized so that the H2 plasma and the Si supplied from the upper electrode plate 24 are only Time acts on the surface of the photoresist layer 163, and on the surface of the photoresist layer 163, a thin protective layer 163b containing Si-O or Si-C is formed (step 5) (Fig. 9B).

That is, it is considered that in the state of this modified example, in the process of the photoresist layer 163, a reaction with C or rhenium on the surface of the photoresist layer 163 occurs, and as a result, it has high reactivity. A state in which most of C or 0 exists on the surface of the photoresist layer 163, and highly reactive C or O reacts with Si supplied by the upper electrode plate 24 to form Si—O or Si—C. Thin protective layer 163b. The thin resist layer 163b containing Si-0, Si_C, or the like improves the plasma resistance of the photoresist layer 163. Next, in the same processing container or other processing container, for example, C5F8, Ar, and 02 are used as an etching gas system (step 16), and the photoresist layer is passed through the same order as that of the organic reflection prevention layer 162, etc. -47- (43) 200401365 1 6 3 opening pattern 1 6 3 a 'Electric etch is performed on the etching target layer 1 6 1 (step 17). Thereby, for example, a high aspect ratio opening 1 6 1 a is formed (FIG. 9C). Next, after the etching of the target layer 161, the object to be processed W is taken out of the processing container through the gate valve 32 (step 18). In the state of the present modification example when the opening pattern 16 of the etching target layer 16 is etched a, as described above, by forming a protective layer 163b on the surface of the photoresist layer, The plasma-resistant state, therefore, maintains the plasma-resistance of the photoresist layer 163 or the selection ratio for etching to a high degree. In addition, in the photoresist layer 1 63, no beryllium cracks or vertical streaks occur, and opening patterns 1 6 1 a due to plasma etching can be formed at a high uranium etch rate. As a result, other unnecessary operations are required, and at the same time, the efficiency of the plasma etching operation is improved. The formation process of the protective layer I 63b in the aforementioned step 15 is H2, so H2, N2, and He may be used together. In addition, in the present embodiment, the etching target layer 1 6 1 is not limited to the Si oxide represented by Si02, and other Si compounds such as Si nitrogen, Si carbide, single crystals, etc. can also be applied. Crystalline organic materials, organic-inorganic hybrid materials, metals, and metal compounds In addition, in this embodiment, it is particularly effective for the exemplified ArF photoresist and photoresist with low plasma resistance, but it is not limited thereto 'Even if the EB resist of photolithography by electron beam, EUV resist and KrF resist of photolithography by vacancy of ultraviolet light are finished, the surface of the mask surface is 163. Since there is no need to produce substitutions for Si 'and so on. The agent may be provided with a photoresist layer of (44) (44) 200401365, and the same effect can be obtained. In addition, the photoresist layer is not limited to the photoresist layer, and may be another cover layer. In addition, the structure of the plasma processing apparatus is not limited to that shown in the first figure. In addition, the upper electrode plate is used as the Si source when the protective layer is formed. However, it is not limited to this, and at least the surface of a processing member such as a focus ring 'shield ring and inner chamber' can be made by Contains Si and is used as the same Si source. However, since the upper electrode plate is disposed to face the object to be processed, there is an advantage in that it is possible to uniformly improve the plasma resistance in the surface of the object to be processed, and as a result, it becomes suitable. Next, an example 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 the following examples and comparative examples are 60 MHz and 13,56 MHz, respectively. (1) [Plasma treatment of photoresist layer] Here, the formation of a photoresist layer covering the opening pattern of the etching target layer and plasma treatment of each H2, N2, and He are performed. Examples 1 to 3 and Comparative Examples of Plasmaization and Plasma Treatment of Ar. The plasma treatment was performed for 1 minute. An ArF photoresist was used as the photoresist layer. (Example 5-1) Pressure in the processing container: 2.01Pa (15mTorr) -49- (45) 200401365

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

High-frequency power from the second high-frequency power source: 100W etching gas and its flow rate: H2 becomes 0.1L / min (lOOsccm) lOOsccm)

(Example 5-2) Pressure in the processing vessel: High-frequency power from the first high-frequency power source etching gas from the second high-frequency power source and its flow rate 2.01Pa (15mTorr): High-frequency power of 2200W: 1 00 w: N2 becomes 0.1 L / min ((Examples 5 to 3)) Pressure in the processing vessel: 2.0 lPa (15 mTor.

High-frequency power from the first high-frequency power source: 22 00 W

High-frequency power from the second high-frequency power source: 100 W. Gas and its flow rate: He becomes 0.1 L / min (100 sccm)

(Comparative Example 5-1) Pressure in the processing container: 2.01Pa (15mTorr)

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

High-frequency power from the second high-frequency power supply: 100W etching gas and its flow rate: Ar becomes 0.1L / min (100sccm). Figures HA and 11B show the photoresist using acrylic and methacrylic ArF photoresist, respectively. The surface analysis results of the photoresist layer immediately after the plasma treatment (by the line graphs indicated by H2'N2, He, Ar) -50- (46) 200401365. As mentioned above, even if it is an acrylic agent, it is a combination of a photoresist layer or Si-C due to the principle. In contrast, even if an ArF photoresist is attached under the condition of the principle. In the photoresist, in this state, the accidental use of H i near the Si is H2, N2 'He = (2) [organic reflection prevention has: an etch stop layer and formation of the object to be treated W Etching was performed, and then the same treatment as in Example 5-1 was performed (9A, 9B, the internal pressure of the processing vessel came from the first high frequency and the second high frequency, and it was observed that in Examples 5-1 to 5-3, A protective layer containing a substance having an energy equivalent to Si-0 exists on the surface of the electric award place caused by the electric emission of any of the ArF photoresist H2, N2, and He based on the acrylic. Based on Comparative Example 5-1 The plasma caused by Ar is made of any of acrylic and methacrylic, and only the surface of the Si layer supplied by the upper electrode plate is observed to adhere to Si to improve the plasma resistance, but after honing, Porosity may occur in the layer to be etched. From this, it is confirmed that it can be processed by plasma treatment.

Plasma treatment of photoresist layer after stop layer etching] For the object layer and the photoresist layer covering the opening pattern of the organic reflection anti-reflection layer of the object layer to be etched, the organic reflection prevention layer is subject to the following conditions In the same manner as in Examples 5-1 to 5-3 and the comparative example, and for the photoresist layer] 6 3, the steps of plasma map and FIG. 10 are performed (1 to 15). Force: 6.7Pa (50mTorr) High-frequency power of the power: 1 000W High-frequency power of the power: 100W

-51-(47) 200401365 Etching gas and its flow rate: CF 4 becomes 0 ″ [/ mi η (1 0 0 sccm) Next, the etching target layer 〖6 1 is etched under the following conditions (Fig. 9C, Steps 16 to 18 in Figure 5) »Pressure inside the processing vessel: 2.01Pa (15mTorr) High-frequency power from the first high-frequency power source: 2170 W High-frequency power from the second high-frequency power source: 1550W Etching gas and its flow rate : C-C5F8: 0.015L / min (15sccm

)

Ar: 0.380L / min (380sccm) 〇2: 0.019L / min (19sccm)

After the etching of the etching target layer 16 I as described above, the cross-sectional shape of the etched portion of each object to be treated was observed by an electron microscope photograph. As a result, almost no photoresist was found in the to-be-processed object by using Η2, N2, He, and Ar for the photoresist layer composed of Ar F photoresist. The surface of the layer is wrinkled or streaked. On the other hand, in the above-mentioned operation, it was found that the surface of the photoresist had cracks or vertical streaks in the object to be treated without plasma treatment of the photoresist layer. In addition, in a state where the photoresist layer is subjected to plasma treatment after the organic antireflection layer is etched and before the etching target layer is etched, the photoresist is performed more than before the organic antireflection layer and the etching target layer are etched. In the state of the plasma treatment of the layer 1 63, the surface of the ArF photoresist layer after the etching of the etching target layer is cracked or the generation of vertical stripes is relatively small. Therefore, if the uranium is etched in the organic reflection prevention layer, a CF4 plasma with a high etching speed and less damage to the ArF photoresist layer is used, and then the plasma of the ArF photoresist layer -52- (48) 200401365 processing, and then, if the etching target layer is etched, the production efficiency and the accuracy of the touch can be improved. (Sixth embodiment)

Here, the plasma processing apparatus 1 shown in FIG. 1 is used to implement: for example, the substrate shown in FIG. 12 has a base material layer 171 made of SiO 2 m, an anti-reflection layer 172 covering the base material layer 71, and a cover reflection is formed. The object W of the opening pattern of the prevention layer 1 72 and the photoresist layer 1 73 composed of an ArF photoresist or an F2 photoresist passes through the opening pattern 173 a of the photoresist layer 1 73, and for the reflection prevention layer 172 To perform plasma etching. Even in this embodiment, as the Ar F photoresist or F 2 photoresist, alicyclic acrylic resin, cycloolefin resin, cycloolefin-maleic anhydride resin, or the like can be used. The anti-reflection layer 62 may be an inorganic or organic material. For example, amorphous silicon or an organic polymer material that is a carbonaceous material can be used.

During etching, first, the gate valve 32 is opened, and the object to be processed W is carried into the processing container 2 and placed on the electrostatic chuck 11. Next, after closing the gate valve 32 ′ to depressurize the inside of the processing container 2 by the exhaust device 35, the valve 28 is opened to supply the aforementioned processing gas, such as C2F4 and O2 gas, from the processing gas supply source 30, This makes the pressure in the processing container 2 a predetermined pressure. In this state, a high-frequency power source is applied to the upper electrode 21 and the sensor 5 ′ serving as the lower electrode, and the process gas is plasmatized, and the opening pattern 173 a of the photoresist layer 173 is transmitted to the object W Nakano53- (49) 200401365

The anti-reflection layer 172 is etched. On the other hand, before and after the high-frequency power is applied to the upper and lower electrodes, a DC voltage is applied to the electrode 12 in the electrostatic chuck Π to electrostatically adsorb the object W on the electrostatic chuck C. During the etching, An end point detector (not shown) detects a predetermined luminous intensity, and the etching is terminated based on this.

In this embodiment, as described above, the anti-reflection layer 1 72 can be etched by using a processing gas containing c2F4, for example, a processing gas containing c2F4 and 02, to pass through the photoresist layer 73 to suppress the photoresist layer 1 The surface of 73 is cracked, and the selection ratio of the antireflection layer to the photoresist layer is maintained at a high level. At the same time, the etching rate of the antireflection layer 1 72 is increased.

In addition, in the present embodiment, the present invention is not limited to the aforementioned embodiment ', and various changes can be made. For example, the state of the anti-reflection layer is shown as an etching target layer, but it is not limited to this, and may be a state in which another layer is etched. In addition, the process gas system containing C2F4 is not limited to those containing C2F4 and 02. In addition, in the state where a processing gas containing C2F4 is used, the cover layer is not limited to ArF photoresist or F2 photoresist. Other photoresists can be used, and even non-resistive cover layers can be used. . In addition, the structure of the uranium engraving device is not limited to that shown in FIG. 1. Hereinafter, an example based on this embodiment will be described. First, the conditions of the examples are as follows. That is, the pressure in the processing trough is made to be 1.33Pa (10mTorr) and 6.66Pa (50mTorr), and the flow rate ratio of c2F4 and 02 of the processing gas is C2F4: 〇2 = 5: 2, 3: 2, 5: 4, 1: 1, 3: 4, high-frequency power of 60MHz is applied to the upper electrode at -54- (50) (50) 200401365 600 '1000, 1400W, and high frequency of 2MHz is applied to the lower electrode at 100W. electric power. On the other hand, the conditions of the comparative example are as follows. In other words, the pressure in the processing vessel is 6.66 Pa (50 mTorr), the processing gas becomes CF4, and high frequency power of 60 MHz is applied to the upper electrode at 1000 W, and high frequency power of 2 MHz is applied to the lower electrode at 100 W. . When etching is performed under such conditions, the selection ratio of the anti-reflection layer to the ArF photoresist cover curtain layer (etching speed of the anti-reflection layer / ArF photoresist cover curtain layer) is in the examples and comparative examples. It is not much different, but the etching rate of the anti-reflection layer is in the embodiment, and becomes 1.2 to 3.6 times that of the comparative example. In addition, not only the comparative examples, but also the examples, the surface cracks of the curtain layer of the ArF photoresist cover did not occur. From this, it was confirmed that the examples can prevent the reflection preventing film from being etched at a high etching rate without causing surface cracks of the ArF photoresist mask layer.

(Seventh Embodiment) Here, using the plasma processing apparatus 1 shown in FIG. 1 described above, it is implemented to have a Si02 layer 181 as an etching target shown in FIG. 13A, and a reflection covering the 3/02 layer 181 The anti-reflection layer 182 and the object to be processed W of the photoresist layer 183 covering the antireflection layer 182 and composed of an ArF photoresist or an F2 photoresist, pass through the opening pattern of the photoresist layer 183] 83a. The operation of etching the layer 1 8 2 is performed; and the operation of etching the Si02 layer 1 8 1 after the operation. Even in this embodiment, if -55- (51) (51) 200401365 is A r F photoresist or F 2 photoresist, alicyclic acrylic resin, cycloolefin resin, cycloolefin- Maleic anhydride resin. As the anti-reflection layer, an organic polymer material or amorphous carbon can be applied. First, the gate valve 32 is opened, and the object to be processed W is carried into the processing container 2 and placed on the electrostatic chuck U. Next, the gate valve 32 is closed, and after the pressure in the processing container 2 is reduced by the exhaust device 35, the valve 28 is opened, and a substance containing C and F and a substance containing C and F are supplied from the processing gas supply source 30. The etching gas of the plutonium substance makes the pressure in the processing container 2 a predetermined plutonium, for example, 6.66Pa (50mTorr). In this state, a high-frequency power source is applied to the upper electrode 21 and the sensor 5 serving as the lower electrode, and the etching gas is used to plasmatize the anti-reflection layer 1 82 (the first 3 A picture). This can increase the amount of residual film of the photoresist layer 1 8 3 after the etching of the anti-reflection layer 1 2 2 is completed, and it is possible to form a hole or groove having a desired opening shape in the next etching operation. groove. As the substance containing C and F used in this etching, CF4 with little damage to the ArF photoresist layer is exemplified. In addition, as the substance system having tritium, hydrogen carbon, H2, and hydrofluorocarbon can be used. Examples of the hydrogen carbon system include CH4 and the like. As a hydrofluorocarbon system, the ratio of the number of Η atoms to the number of F atoms 値 is preferably 3 or more. As such a material system, CH3F is exemplified. In the state where CH3F is used, the ratio 流量 of the flow rate of CH3F in the etching gas to the flow rate of the substance having C and F can be 0.0 4 to 0. 〇7 ', compared with when no CH 3 F is added at all, The amount of the residual film of the ArF photoresist layer after the etching of the antireflection layer is also increased considerably. -56- (52) (52) 200401365 On the other hand, before and after the time of applying high-frequency power to the upper and lower electrodes, apply a DC power source I 3 to the electrode 1 2 in the electrostatic chuck 11 to statically treat the object W Adsorbed on the electrostatic chuck 1 1. If the etching of the reflection preventing layer 182 is finished in this way, the supply of the etching gas or high-frequency power m is stopped. Next, in the processing container 2, another etching gas such as a mixed gas of C5F8, 02, and Ar is supplied, and the pressure in the processing container 2 is adjusted to, for example, 2.00 Pa (15 mTorr). A high-frequency power source is applied to the upper electrode 21 and the sensor 5 serving as a lower electrode, and the etching gas is plasmatized to etch the Si02 layer 181 in the object W (Fig. 13B). In the etching, an end point detector (not shown) detects a predetermined luminous intensity, and the etching is terminated based on this. In addition, the etching target system is not limited to the above-mentioned Si02 film, and may be applied to oxide films such as TEOS, BPSG, PSG, SOG, thermal oxide film, HTO, FSG, organic silicon oxide film, and CORAL (Novaveas) (Oxygen compound) or low dielectric organic insulating film. In addition, the structure of the plasma etching apparatus to be applied is not limited to that shown in FIG. 1. Next, an example based on this embodiment will be described. The treated system used the SiO2 layer (film thickness 2 / im) of Figure 13A, the anti-reflection layer (film thickness 60nm) covering the SiO2 layer, and the ArF photoresist layer (film thickness 360nm) covering the anti-reflection layer. )By. The etching conditions of the anti-reflection layer in the examples are as follows. In other words, the pressure in the processing container 2 is 6.66Pa (50mTorr), -57- (53) 200401365 will be engraved into CF4 (flow rate 100mL / min (sccm)) and CH3F (flow rate 4 or 7mL / min ( sccm)), a high frequency power of 60 MHz is applied to the upper electrode by a high frequency power source of 60 MHz and a high frequency power of 2 MHz is applied to the lower electrode by a high frequency power of 1 000 W. electric power. In addition, even when using H2 (flow rate 5'10 or 15mL / min (sccm)), CH2F: z (flow rate 5 or 10mL / min (sccm)), and CHF3 (flow rate 10, 30, 50, or An etching gas of 70 mLX min (seem)) was also similarly etched.

In the comparative example, the etching gas was made to only CF4 (flow rate 100 mL / min (s c c m)), and other conditions for etching were the same as in the embodiment. The antireflection film 182 was etched under the conditions of the above examples and comparative examples, and the following results were obtained when the residual film thickness of the ArF photoresist layer was measured after a certain etching time. In the example, under the condition that CH3F is used, the thickness is 37.5 5 nr η at a flow rate of 4mL / min, and 4 05 nm at 7 m L / min. In the state that h2 is used, the thickness is at the flow rate 5 m] L / mi n becomes 3 4 5 nm, at 10 m L / mi η and 15 m L / min, it becomes 3 6 0i lm ο When using ch2f2, the thickness is at the flow rate of 5 m L / mi n becomes 3 4 5 n rr, where] L 0 m L /] mi r 1 becomes 4 0 nm 〇 In the state of chf3 for i, the thickness is at a flow rate of 10 mL / min to 350 nm 'at 30 mL / min becomes 3 6 Onm, it becomes 3 6 Onm at 50 m L / mi η, and it becomes 3 90 nm at 70 m L / mi η. On the other hand, in the comparative example, the thickness is 330 nm.

From the above, it was confirmed that even in any of the embodiments, the thickness of the residual film was increased more than that of the comparative example. It is thought that this is because the F-activated species of the photoresist layer etched ArF -58- (54) 200401365 and the H-activated species generated from the gas have reacted moderately to become a gas such as HF and discharged to the outside of the processing container. The reason.

In addition, the 'C Η 3 F system is particularly good even in these examples. It is thought that whether the flow rate of ch3f becomes small and the amount of residual film increases is because the number of plutonium atoms in the molecule is more than the number of F atoms = However, for example, a chemically stable substance in plutonium 2 is presumed to be more active than that even if plutonium is generated When the species reacts with the F-activated species, it is advantageous to react with other Η-activated species to perform a recombination system. The amount of the residual membrane system is not more than that of other substances.

Therefore, it is confirmed that the substance itself can be present to a certain degree of instability and there are many plutonium atoms in the substance such as hydrogen carbon (CH4, C2H4, etc.) or hydrofluorocarbon (especially the ratio of the number of atom to the number of F atom 原子 3 The above, for example, C Η 3 F) and the like are added to the etching gas. In addition, it was confirmed that, in the case of using CH3F, even if the ratio of the flow rate of CH3F to the flow rate of CF4 which is a substance having C and F is 0.04 to 0.07, the amount of residual film can be increased. (Eighth Embodiment) Here, using the plasma processing apparatus 1 shown in FIG. 1 described above, it is implemented that the Si02 layer 191 having a layer to be etched as shown in FIG. 4A is covered with the 5 丨 02 layer 191 The antireflection layer 192 and the object W of the photoresist layer 193 covering the antireflection layer 192 and composed of an ArF photoresist or an F2 photoresist pass through the opening pattern of the photoresist layer 193- 59- (55) (55) 200401365 1 93 a 'For the anti-reflection layer! The operation of etching is performed at 92; and the operation of etching the Si 02 layer 9 1 after this operation is performed. Even in the fifth embodiment, the "As A F photoresist and F 2 photoresist" system can also use alicyclic propionic acid resin, cyclophosphine resin, cyclophosphine-cis butadiene Acid liver resin. As the anti-reflection layer ', an organic polymer material or amorphous carbon can be used. First, the "open gate valve 32" carries the object to be processed W into the processing container 2 "and is disposed on the electrostatic chuck 11. Next, the gate valve 32 is closed, and after the inside of the processing container 2 is depressurized by the exhaust device 35, the valve 2 8 'is opened to supply a substance containing C and j: from the processing gas supply source 30 and The first etching gas of CO, for example, a mixed gas of CF4 and CO, makes the pressure in the processing vessel 2 a predetermined pressure, for example, 3.3 Pa (100 m Torr). In this state, a high-frequency power source is applied to the upper electrode 21 and the sensor 5 serving as the lower electrode, and the first uranium-etched gas is plasmatized to etch the anti-reflection layer in the object to be treated. 1 4A). On the other hand, before and after the high-frequency power is applied to the upper and lower electrodes, a DC power source 3 is applied to the electrode 12 in the electrostatic chuck 11 to electrostatically adsorb the processing object W on the electrostatic chuck 11. When the etching of the anti-reflection layer 192 is finished, the supply of the first etching gas and high-frequency power is stopped. Then, in the processing container 2, a second etching gas such as a gas containing fluorocarbon such as c5f8 and c4f6 is supplied. Specifically, it is a mixed gas of c5f8 or c4f6 and 〇2 and Ar, and the pressure in the processing container 2 is adjusted to a predetermined value of the second etching gas, for example, 2.00Pa (15mTorr). A high-frequency power source is applied to the upper electrode 60-1 (56) 200401365 and the sensor 5 serving as the lower electrode, and the second etching gas is plasmatized to etch the Si02 layer 191 in the object W ( (Figure MB). In the etching, a predetermined luminous intensity is detected by an end point detector (not shown), and the etching is terminated based on this. In addition, the etching target system is not limited to the aforementioned Si 02 layer, and can also be applied to TEOS, BPSG, and PSG. , SOG, thermal oxide film, HTO 'fSG, organic silicon oxide film, CORAL (Novelas), etc.

Etching of chemical film (oxygen compound) or low dielectric organic insulating film. In addition, the structure of the plasma etching apparatus to be applied is not limited to that shown in Fig. 1. Next, an example based on this embodiment will be described.

Use the MA map as the processed system. The first etching conditions in the examples are as follows. That is, the pressure in the processing container 2 is 6.66 Pa (50 mTorr) or 1 3.3 Pa (100 mTorr), and the flow rate of the first etching gas becomes CF4: 75, 100, or 200 mL / min (sccm), CO: 25, 100 or 200mL / mixi (sccm), apply 1000 '1500 or 2000W high-frequency power to the upper electrode' from a high-frequency power source of 60MHz frequency, and apply 100W high-frequency power to the lower electrode 'from a 2MHz frequency high-frequency power source . The first etching conditions of the comparative example are as follows. In other words, the pressure in the container is set to 6.66 Pa (50 mTorr). As the first etching gas system, c F 4 (without C 0) is added only at a flow rate of 100 m L / min (sccm). The frequency and applied power are the same as in the embodiment. -61-(57) 200401365 The second etching conditions of Examples and Comparative Examples are as follows. In other words, the pressure in the processing valley is 2.00Pa (15mTorr), and the flow rate of C 5 F 8, 0, and A 2 of the second uranium-engraved gas is 〖5, 19, and 380mL / min (sccm) respectively. In the upper electrode, a high-frequency power of 2170W is applied by a high-frequency power source of 60MHz frequency, and in a lower electrode, a high-frequency power of 1550W is applied by a high-frequency power source of 2MHz frequency. Under the above conditions, the first etching and the second etching were performed. As a result, the selection ratio of the Si 02 layer to the ArF photoresist layer in the second etching operation (etching speed of the Si02 layer / ArF photoresist mask layer) The etching rate) of the example greatly exceeds that of the comparative example. For example, under the first etching condition of the embodiment, a pressure: 13.3 Pa (100 mTorr), a CF4 flow rate: 75 mL / min (seek), a CO flow rate: 25 mL / min (seek), and an upper electrode applied power: 1 000 W. 9.7, the aforementioned selection ratio of the comparative example is 6.3 ^

In addition, when C4F6 is used in place of C5F8 of the second etching operation, the foregoing selection ratio example (the first etching gas system C F 4 and C 0) exceeds the comparative example (the first etching gas system only C F4). In addition, it is considered that a protective film having an inter-carbon bond is formed on the surface of the ArF photoresist layer by a plasma including a substance having C and F and a gas of C 0. The surface of the photoresist layer is irradiated with a plasma containing a substance having C and F and a gas of CO to improve the plasma resistance of the ArF photoresist layer. In addition, the present invention can also be applied to, for example, an ArF photoresist layer other than an ArF photoresist layer that does not have the effect of improving the plasma resistance like the state of an ArF photoresist layer. The second etching gas system is not limited to a gas containing C5F8 or C4F6, and a gas containing other fluorine-containing compounds such as fluorocarbon and hydrofluorocarbon may be used. (Ninth Embodiment)

Here, using the plasma processing apparatus 1 shown in FIG. 1 described above, the organic reflection of the Si 02 layer 2 0 1 having the etching target shown in FIG. The preventive layer 2 02 and the object to be processed W forming a photoresist layer 203 that covers the organic reflection preventing layer 2 02 with an opening pattern 2 03 a and is made of an ArF photoresist or an F2 photoresist, pass through the photoresist layer For the opening pattern of 03, plasma etching is performed for the organic reflection prevention layer 202; and, for the Si02 layer 201, plasma etching is performed. Even in this embodiment, as the ArF photoresist and the F2 photoresist, alicyclic acrylic resins, cycloolefin resins, and cycloolefin-maleic anhydride resins can be used. The organic reflection preventing layer 202 is formed of, for example, an organic polymer material. First, the gate valve 32 is opened, and the object to be processed W is carried into the processing container 2 and placed on the electrostatic chuck Π. Next, the gate valve 32 is closed, and the inside of the processing container 2 is depressurized by the exhaust device 35. Then, the valve 28 is opened, and an etching gas containing SiF4 which is a Si-containing substance is supplied from the processing gas supply source 30. This makes the pressure in the processing container 2 a predetermined pressure. In order to replace SiF4, other materials containing Si may be used. However, from the viewpoint of making the etching rate of the organic reflection prevention layer 202 -63- (59) (59) 200401365 large, it is preferable S i F4. In addition to the Si-containing substance, the etching gas 'may include CHF3, HBr, He, or H2'. For example, SiF4 and H2 are used. In this state, high-frequency power is supplied from the first and second high-frequency power sources 40 and 50, and the etching gas is plasmatized. The opening pattern 203a of the photoresist layer 203 is used to prevent the organic reflection layer. 202 to perform etching. On the other hand, before and after the high-frequency power is applied by the first and second high-frequency power sources 40 and 50, a DC voltage is applied to the electrode 1 2 ′ in the electrostatic chuck 11 to electrostatically adsorb the subject w. On the electrostatic chuck π. If the etching is performed only at a predetermined time, the supply of high-frequency power or etching gas is stopped, and the etching of the organic reflection preventing layer 202 is ended. An end point detector (not shown) can be used to detect a predetermined luminous intensity ' Next, in the same processing container or other processing container, 'pass the opening pattern of the photoresist layer 2 0 3 a in the same order as the etching of the organic reflection prevention layer 2 02, and for the Si 2 layer 2 0 1 to perform plasma uranium engraving. As the etching gas system at this time, for example, C4F6, 02, and Ar 'can be used, but is not limited thereto. As described above, when plasma etching is performed on the organic reflection preventing layer 202 through the opening pattern of the photoresist layer 203, Si F4 gas, which is a gas containing Si, is used. Therefore, the photoresist can be used in the photoresist during etching. Forming a thin hardened layer including Si on the surface of the agent layer 203 can improve the plasma resistance of the photoresist layer 203. Therefore, 'the surface crack or vertical streak does not occur when the organic antireflection layer 202 is etched', it can be maintained to a high degree by the plasma resistance _ 64-(60) 200401365. ArF photoresist or F2 photoresist with low resistance Plasma resistance of the photoresist layer 203. In this state, in a state where the etching gas of the organic antireflection layer 202 contains H2, the C = 0 bond on the surface of the photoresist layer 203 is chemically converted into a strong CC bond or c = c bond, so As the thin hardened layer containing Si is formed on the surface of the photoresist layer 203, the plasma resistance can be further improved.

In addition, after the organic antireflection layer 202 is etched in this manner, the Si02 layer 201 which is an etching target layer is etched through the opening pattern of the photoresist layer 203. Therefore, when the organic antireflection layer 202 is etched, the electric resistance is improved The slurry-based photoresist layer 203 is highly plasma-resistant even if it is plasma-etched in the Si 0 2 layer 2 01, which is the subject of etching, and does not cause surface cracks or vertical stripes on the photoresist layer. Occur, plasma etching can be performed.

In addition, the layer to be etched is not limited to the Si oxide represented by the aforementioned Si 02. For example, other si compounds such as Si nitride, Si carbide, single crystal Si, polycrystalline Si, Organic materials, organic-inorganic hybrid materials, metals' metal compounds, etc. In addition, the structure of the plasma processing apparatus is not limited to that shown in the first figure. Next, an example based on this embodiment will be described. Here, using the object to be processed having the structure shown in FIG. 5, etching is performed using an organic reflection preventing layer having various etching gases containing a substance Si (Examples 9 to 1 to 9 to 7) and using no Etching of an organic reflection preventing layer of an etching gas made of Si (Comparative Examples 9-1, 9-2). The frequencies of the first high-frequency power source and the second high-frequency power source in each of the Examples and Comparative Examples are -65- (61) 200401365. The frequencies of the sources are 60 MHz and 13.56 MHz, respectively. In addition, after the etching of the organic reflection preventing layer in each of the Examples and Comparative Examples under the following conditions, plasma etching of the SiO 2 layer was performed under the etching conditions described later. Etching of the organic reflection preventing layer (Example 9-1) Pressure in the processing container: 0.67 Pa (5 mTorr)

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

High-frequency power from the second high-frequency power source: 60W etching gas and its flow rate: SiF4 becomes 0.08L / min (80sccm) (Example 9-2) Pressure in the processing vessel: 6.7Pa (50mT〇rr)

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. SiF4 becomes 0.1L / min (100sccm) (Example 9_3) Pressure in the processing vessel · · 67Pa (5mT〇rr)

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

High-frequency power from the second high-frequency power source: 60 W etching gas and its flow rate: SiF4 becomes 0.04L / min (40SCcm) and CHF3 becomes 0.04L / min (40sccm) -66-(62) 200401365 (Implementation Example 9-4) Pressure in the processing container: 0.67Pa (5mTor.

High-frequency power from the first high-frequency power source: 300W High-frequency power from the second high-frequency power source: 60 w Etching gas and its flow rate: SiF4 becomes 0.4L / min (40sccm) HBr becomes 0.4L / min (40sccm) (Examples 9 to 5) Pressure in the processing vessel: 0.67Pa (5mTorr)

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

High-frequency power from the second high-frequency power source: 60W etching gas and its flow rate. SiF4 becomes 0.4L / min (40sccm)

He becomes 0.04L / min (40sccm) (Example 9-6)

Pressure in the processing vessel · · 67Pa (5mT〇rr)

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

High-frequency power from the second high-frequency power source: 60 W etching gas and its flow rate: SiF4 becomes 0.04L / min (40sccm) HBr becomes 0.02L / min (20sccm)

He becomes 0.02 L / min (20 sccm) (Example 9-7) -67- (63) 200401365 Pressure in the processing vessel: 6.7Pa (50mT〇rr) High-frequency power from the first high-frequency power source: 〖〇〇〇〇 W Local-frequency power from the second commercial frequency power supply: 100W etching gas and its flow rate: SiF4 becomes 0.03L / mi H2 becomes 0.02L / min (30 sccm) 2 0 sccm) (Comparative Example 9-1) Processing Pressure in the container: 0.93 Pa (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: CF4 becomes 0.072L / mi CHF3 becomes 0.026L / min (26sccm) 〇2 becomes 0.006L / min (6sccm) (Comparative Examples 9-2) Pressure in the processing vessel: 6.7Pa (50mTorr) High-frequency power from the first high-frequency power source: 1000W from the second High-frequency power of high-frequency power supply: 100W etching gas and its flow rate: CF4 becomes 0.1 L / min (etching of Si02 layer (Examples 9-1, 9-3 to 9-6, and Comparative Example 9-1) η (7 2 sccm) 1 0 0 sccm) -68-(64) 200401365 Pressure in processing vessel: 6Pa (120mTorr) High-frequency power from the first high-frequency power source: 550W High-frequency power from the second high-frequency power source: 350W etching gas and its flow rate: CF4 becomes 0.1L / min (100sccni) CHF3 becomes 0.06L / min (60sccm) (Example 9-2 '9-7 and Comparative Example 9 —2) Pressure in the processing vessel: 2.7Pa (20mT〇rr)

Commercial frequency power from the first local frequency power supply: 1800W High frequency power from the second high frequency power supply: 1150W Etching gas and its flow rate: C4F6 becomes 0.02 5 L / min (25SCCm) 〇2 becomes 〇26〇 / L 26sccm)

Ar becomes 0.7L / min (700sccm)

As described above, after the SiO2 layer 201 is etched, the cross-sectional shape of the etched portion of the object w to be treated in each of the Examples and Comparative Examples is observed by an electron microscope photograph. As a result, in Examples 9-1 to 9-7, almost no surface wrinkles or vertical streaks were observed in the ArF photoresist layer 203. However, in Comparative Examples 9-1, 9-2, ArF was found. The surface of the photoresist layer 203 has wrinkles or vertical stripes. (Embodiment 10) Here, as shown in FIG. 16A, the etching target layer 2 1 1 having the Si oxide represented by the Si 02 film and the etching target layer -69- (65) (65) 200401365 2 1 1 and the object W of the cover layer 2 1 2 composed of an ArF photoresist or an F2 photoresist, using the electric paddle processing device shown in FIG. 1 to implement a series of operation. Even in this embodiment, as the ArF photoresist or F2 photoresist, alicyclic acrylic resin, cycloolefin resin, cycloolefin-maleic anhydride resin, and methacrylic resin can be used. In this embodiment, even in the shower head of the device of Fig. 1, a certain upper electrode plate 24 is formed of Si. First, the gate valve 32 is opened, and the object to be processed W is carried into the processing container 2 and placed on the electrostatic chuck 11. Next, the gate valve 3 2 ′ is closed, and after the pressure in the processing container 2 is reduced by the exhaust device 35, the valve 28 is opened, and an inert gas such as Ar ′ is supplied from the processing gas supply source 30 so that the processing container 2 is inside. The pressure is, for example, 1.33 Pa (0 mTorr). As the inert gas system, other gases such as Kr and Xe can be used. In this state, high-frequency power is applied to the upper electrode 21 and the sensor 5 serving as the lower electrode by high-frequency power sources 40 and 50, respectively, and at least a portion of the inert gas is ionized. The upper electrode plate 24 composed of S i is subjected to sputtering. On the other hand, before and after the high-frequency power is applied to the upper and lower electrodes, a DC power source 13 is applied to the electrode 12 in the electrostatic chuck 11 to electrostatically adsorb the object W on the electrostatic chuck 1. At this time, the high-frequency power applied to the upper electrode 21 is the energy that promotes the ionization of the inert gas. The upper electrode plate 24 made of Si can be sputtered in this way, and as shown in FIG. 16B, the Si-containing layer 213 is formed on the surface of the mask 餍 212. When the time for forming the Si-containing layer 2 1 3 on the surface of the mask layer 212 is too short, there is no effect of increasing plasma resistance -70- (66) (66) 200401365. A plurality of Si-containing layers are formed on the surface of the etching target layer 2 1 1 at the opening portion of the curtain layer 212, which hinders subsequent etching. Therefore, it is preferable to select an appropriate time. For example, the conditions of a high-frequency power frequency applied to the upper electrode 21: 60 MHz, power: 2000 W, a high-frequency power frequency applied to the sensor 5: 2 MHz, and power: 1 0 0 W may be used. However, under these conditions, 'The aforementioned processing time is preferably in the range of 60 to 90 seconds. In addition, in terms of electric power, compared with a state where the applied power of the upper electrode is I 250 W and the applied power of the sensor is 400 W (a state where the V PP is reduced), the aforementioned conditions can reduce the cover when the Si-containing layer is formed. Changes in the shape of the opening of the curtain layer. When the VPP is too high, the opening of the mask layer is enlarged, and it is impossible to make holes or grooves of the opening pattern designed for subsequent etching operations. When the formation of the Si-containing layer on the surface of the mask layer is completed, the application of high-frequency power is stopped. Then, an etching gas is introduced into the processing container 2, high-frequency power is applied to the upper electrode 21 and the sensor 5, and the etching target layer 2 is etched. For example, in a state where the etching target layer 2 1 1 is formed of Si oxide, it is preferable to include at least one gas selected from C4F6, C4F8, and C5F8. Examples of such an etching gas system include a mixed gas of C4F6, 02, and Ar. In addition, it is also exemplified that the pressure in the processing container 2 becomes 2.67 Pa (20 mTorr), and the high-frequency power applied to the upper electrode 21 and the sensor 5 becomes 1600 W and 800 W, respectively. The frequency of the high-frequency power at this time is the same as that when sputtering, and 60 MHz and 2 MHz are exemplified. The etching gas is plasmatized by applying high-frequency power -71-(67) 200401365, and the etching target layer 2 1 made of, for example, si oxide is etched. When the etching is completed, the application of the etching gas and high-frequency power is stopped.

When the etching target layer 2 1 1 made of Si oxide is etched under the conditions exemplified above, the selection ratio of the etching target layer 2 1 1 to the mask layer 2 1 2 (uranium etch rate of the etching target layer / The etching rate of the cover layer is 2 8.8. The above-mentioned selection ratio is 8.2 when the etching of the Si-containing layer on the surface of the mask layer 212 is not performed. After the etching is performed in this manner, an operation (honing operation) of removing the mask layer 212 forming the Si-containing layer 213 on the surface is performed next. Here, an example is shown in a state in which the cover layer 2 1 2 of the Si-containing layer 2 1 3 is formed on the surface in multiple stages.

In the first stage, a fluorine-containing gas such as CF 4 is introduced into the processing container 2. At a predetermined time, high frequency power is applied to the upper electrode 21 and the sensor 5, and the cover layer 212 is almost completely removed. Of Si containing layer 213. When the Si-containing layer remains, in the next second stage, when the mask layer 212 is removed, the Si-containing substance adheres to the surface of the object to be processed. At this time, for example, the pressure in the processing container 2 becomes 6.66Pa (50mTorr), and the high-frequency power applied to the upper electrode 21 and the sensor 5 becomes 1600W and 800W, respectively, and the frequency is the same as that during sputtering and becomes 60MHz. , 2MHz. The Si-containing layer 213 can be removed almost completely by performing a treatment under this condition, for example, for 90 seconds. In addition, in a state where a gas of 0 2 and Ar is added to CF4 as the gas at this time, the cover layer 2 1 2 -72- (68) 200401365 made of an ArF photoresist is damaged. Therefore, it is desirable to use a gas of CL alone or to add CF2 or Ar or the like to a small amount. Gases other than CF4 can be used as the gas system containing fluorine compounds. However, if the mask layer 2 1 2 made of an ArF photoresist for the Si-containing layer 213 substrate is used, the damage is reduced. , It is best to use CF4.

In the second stage, a predetermined process gas is introduced, and high-frequency power is applied to the upper electrode 21 and the sensor 5 serving as the lower electrode to remove the mask layer 212 itself after removing most of the Si-containing layer 213. At this time, as the processing gas system, it is preferable to use a gas not containing a fluorine compound, such as a single gas of 〇2 'or a mixed gas containing 〇2 and N2 or Ar, or a mixed gas of 〇2, N2, and Η2. .

The processing of this second stage is actually performed. In this state, the pressure, high-frequency power, and high-frequency power are the same as those in the first stage example without any change, and only the processing gas is changed to perform honing. Here, 〇2 is used. When observing the object to be treated with the mask layer 212 removed, the opening shape and cross-sectional shape of the holes or grooves were almost as designed. In addition, adhesion of the Si-containing substance to the object to be treated did not occur. In the present embodiment, as described above, the inert gas is ionized by the energy at the time of applying high-frequency power to the parallel flat-plate electrode, thereby sputtering the upper electrode plate 24 made of Si and attaching it to the cover. Since the Si-containing layer is formed on the surface of the curtain layer 212, the plasma resistance can be improved considerably compared to when the curtain layer itself is covered. Especially when using ArF photoresist or F2 photoresist with low plasma resistance as the cover layer 2 1 2 -73- (69) (69) 200401365 the effect of improving the plasma resistance becomes Significant. In addition, honing after etching is performed on the object layer to be etched, and the Si-containing layer 213 is removed and the mask layer 212 itself is removed in multiple stages. Therefore, even when the Si-containing layer 2 is formed, In the state of 13 and the cover layer, the properties suitable for each layer can also be removed. Of course, it is also possible to remove the Si-containing layer 213 and the mask layer 212 at one time. Regardless of whether or not any one is used, the decision can be made by comparing the advantages and disadvantages of the removal in multiple stages and the removal in one step. In addition, the target system when the cover layer is formed on the cover layer by sputtering is not limited to the above-exemplified upper electrode plate, and if it is a member that is disposed in the processing container and whose surface becomes at least a part of S i , It can be other components such as the focus ring, or a Si component can be configured as a new target. In addition, other Si wafers (bare wafers) without component processing can be placed in a processing container and used as targets. In addition, the use of S i as a target enables sputtering of a single crystal S i. In addition, in the foregoing example, a parallel flat plate device for plasma etching was used to perform sputtering using high-frequency energy. However, the invention is not limited to this, and it is also possible to use one that imparts energy to at least a part of the inert gas for ionization. For example, the energy system is not limited to high-frequency energy, and microwave energy may be used. In addition, even in a state where high-frequency energy is used, it is different from the aforementioned parallel flat plate, and a method of applying a high-frequency power to form an inductive delta field can be used. In addition, the method of forming the Si-containing layer 213 on the surface of the mask layer 212 is (74) (70) (70) 200401365, and the method is not limited to sputtering. For example, the Si-containing layer 213 can be formed on the surface of the mask layer 2 1 2 by CVD. In the state where the Si-containing layer 2 1 3 is formed by CVD, as the gas system to be used as the raw material, an organic stone-based gas or an inorganic sand-based gas can be used. However, an inorganic sand-based gas is preferred. The CVD in this state can be performed in the usual manner using these gases. As a method for forming the Si-containing layer 213 on the surface of the mask layer 212, a method in which an Si compound such as SiF4 is added to the etching gas may be used. This can be used to simultaneously improve the plasma resistance of the mask layer 2 1 2 composed of the Ar F photoresist or the F 2 photoresist and the etching of the etching target layer 2 1 1. In this embodiment, the layer to be etched is not limited to the above-mentioned Si oxide, and various materials such as SiC, SiN, organic low-dielectrics, SiF, metals, and metal compounds can be applied. However, since the layer formed on the surface of the mask layer has Si as a main component, it is not easy to apply it to a subject to be etched in which the layer becomes Si. When the surface of the mask layer and the layer to be etched are made of the same material, the etching rate is almost the same. In addition, the mask layer is not limited to ArF or F2 photoresist materials with low plasma resistance. It can be other organic photoresist layers, not even limited to photoresist. It is the other cover layer. [Brief description of the drawings] Figure 1 is a cross-sectional view showing an example of a plasma processing apparatus that can implement the plasma processing method of the present invention; -75- (71) (71) 200401365 Figure 2 shows that the present invention can be implemented Sectional view of another example of the plasma processing apparatus of the plasma processing method of the invention; FIG. 3 is a cross-sectional view schematically showing the object to be processed used in the treasure application of the first embodiment of the present invention; 4A, 4B The diagram is a sectional view schematically showing the state of the object to be used in the implementation of the second embodiment of the present invention in accordance with the work sequence. The diagrams 5A and 5B are diagrams schematically showing the use in the present invention in accordance with the work sequence. Sectional view of the state of the object to be processed in the implementation of the third embodiment. Figures 6A, 6B, and 6C are diagrams schematically showing the state of the object to be used in the implementation of the fourth embodiment of the present invention in the order of operations Sectional views; Sections 7A, 7B 'and 7C are sectional views schematically showing the state of the object to be used in the implementation of the fifth embodiment of the present invention in accordance with the operation sequence; and FIG. 8 is a view showing the fifth of the present invention A series of implementations 9A '9B and 9C are sectional views schematically showing the state of the object to be used in the implementation of the modified example of the fifth embodiment of the present invention in accordance with the operation sequence; FIG. 10 is a diagram Shows a flow chart of fun string operation, one of the modified examples of the fifth embodiment of the present invention; Figures IA and 11B show the implementation of the fifth embodiment of the present invention. -76- (72) 200401365 The graph of the effect; Fig. 12 is a cross-sectional view schematically showing the object used in the implementation of the sixth implementation # # of the present invention; Figs. 1 3 A and 1 3 B are schematically displayed in accordance with the operation sequence The state of the object to be used in the implementation of the seventh embodiment of the present invention = ^ ® Figures; Figures 14 A, 14B are shown schematically in accordance with the order of operations. &Amp; Eighth embodiment of the invention _ @ State of the object to be processed during implementation; Figures 15 to 15 are schematic cross-sectional views of the object to be used in the implementation of the ninth embodiment of the present invention; Figures 16A, 16B, and 16C are The tenth embodiment used in the present invention is schematically shown in the order of operations. Sectional view of the state of the object to be processed in the state implementation. [Illustration of drawing number]

W: to-be-processed body 1: plasma processing device 2: processing container 3: insulator 5: sensor 6: high-pass filter (HPF) Π: electrostatic chuck 1 2: electrode-77- (73) 200401365 1 3: DC power supply 1 5: Focusing ring 2 1: Upper electrode 24: Upper electrode plate 2 5: Support

26: Gas inlet 2 7: Gas supply pipe 28: Valve 2 9: Mass flow controller 3 0: Process gas supply source 3 1: Exhaust pipe 3 2: Gate valve 3 5: Exhaust device 40: First station frequency Power 4 1: Integrator

4 2: Low-pass filter 50: Second local frequency power supply 51: Integrator 6 I: Plasma etching device 6 2: Processing container 6 2 a: Upper 6 2 b: Lower 6 3: Insulator 6 5: Sensor -78- (74) (74) 200401365 7 1: Electrostatic chuck 72: Electrode 73: DC power supply 7 5: Focusing ring 8 1: Upper electrode plate 82: Multi-pole ring magnet 86: Gas inlet 8 7: Gas supply Pipe 8 8. Valve 89: Mass flow controller 90: Process gas supply source 91: Exhaust pipe 9 5: Exhaust device 1 00: Integrator 1 0: First high-frequency power source 102: Second high-frequency power source 1 2 1: S i Ο 2 film 1 2 2: photoresist layer 131: Si02 film 1 3 2: antireflection film 1 3 3: photoresist layer] 41: Si02 film 142: antireflection film 143: photoresist Layer -79- (75) (75) 200401365 1 4 3 a: Opening pattern 1 5 1: Si02 film) 52: Antireflection film 1 5 3: Photoresist layer 1 5 3 a: Opening pattern 1 6 1: Etching Object layer 161a: opening pattern 162: organic reflection preventing layer 1 6 3: photoresist layer 16 3a-opening pattern 1 6 3 b: protective layer 1 71: substrate layer 172: antireflection film 1 7 3: photoresist Layer 17 3a: Opening pattern 181: Si〇2 film 1 8 2: Anti-reflection film 1 8 3: Photoresist layer 1 8 3 a: Opening pattern 191: Si02 film 192: Antireflection film 1 9 3: Photoresist layer 1 93a: Opening pattern 201: SiCh film -80- (76) (76) 200401365 2 02: Organic reflection preventing film 203: Photoresist layer 2 0 3a: Opening pattern 2 1 1: Etching target layer 212: Mask layer 213: Si-containing layer

Claims (1)

(1) (1) 200401365 Patent application scope 1. A plasma processing method, comprising: preparing an object to be treated with an organic layer on the surface; and irradiating the object to be treated with H2 plasma. Operation for improving the plasma resistance of the organic layer. 2. The plasma treatment method according to item 1 of the scope of patent application, wherein the organic layer is a cover layer. 3. The plasma treatment method according to item 2 of the scope of the patent application, wherein the mask layer is a photoresist layer. 4. The plasma treatment method described in item 3 of the scope of the patent application, wherein the photoresist layer is composed of an ArF photoresist or an F2 photoresist. 05. A plasma treatment method, which is characterized by In order to have the operation of preparing a to-be-processed object having an organic layer on the surface, and irradiating the to-be-processed object with a plasma containing a processing gas containing H2 and an inert gas to improve the plasma resistance of the organic layer. 6. The plasma treatment method as described in item 5 of the scope of patent application, wherein the organic layer is a cover layer. 7. The plasma treatment method according to item 6 of the scope of patent application, wherein the mask layer is a photoresist layer. 8 · The plasma treatment method described in item 7 of the scope of patent application, wherein the photoresist layer is composed of an ArF photoresist or F2 photoresist. 9 · As described in item 5 of the scope of patent application Plasma processing method, wherein the aforementioned processing gas system contains N2 = -82- (2) (2) 200401365 10. A plasma processing method, comprising: preparing an object to be treated with an organic layer on the surface; and irradiating the object to be treated with a substance containing tritium The operation of improving the plasma resistance of the organic layer with a plasma of a processing gas and an inert gas = π. The plasma processing method described in item 10 of the patent application scope, wherein the organic layer is a cover layer. 1 2 The plasma processing method according to item 11 of the scope of patent application, wherein the mask layer is a photoresist layer. 1 3. The plasma treatment method as described in item 10 of the scope of patent application, wherein the aforementioned substance having Η is NΗ3. 14. The plasma processing method as described in item 10 of the scope of patent application, wherein the aforementioned processing gas system includes N2. 15 · A plasma processing method, comprising: preparing a surface of a processed object having a photoresist layer composed of an ArF photoresist or F2 photoresist on a surface, and irradiating the processed object The operation of improving the plasma resistance of the photoresist layer by including a plasma of a processing gas having a substance of thallium. 16. The plasma processing method according to item 15 of the scope of patent application, wherein the aforementioned substance having Η is Η2. 17. The plasma processing method according to item 15 of the scope of patent application, wherein the aforementioned substance having Η is N 系 3. 18. The plasma processing method as described in item 15 of the scope of patent application, wherein the aforementioned processing gas system includes N2. 1 9. The plasma treatment method as described in item 15 of the scope of the patent application, -83- (3) (3) 200401365, where the plasma irradiation operation is performed under a pressure of 13.3Pa (100 mTorr) or less Under the atmosphere. 20. The plasma treatment method as described in item 19 of the scope of the patent application, wherein the aforementioned plasma irradiation operation is performed under an atmosphere under a pressure of 1 to 4.0 P a (; 8 to 30 mT0rr). Implementation. 2 1. The plasma processing method as described in item 19 of the scope of patent application, wherein the method has the following operations: the system to be processed has an etching target layer under the photoresist layer, and the photoresist system has an opening pattern After the plasma irradiation, the opening pattern of the photoresist layer is transmitted, and plasma etching is performed on the etching target layer. 22. A plasma processing method, comprising: arranging a processing object having a uranium-engraved object portion and an organic layer covering the etching object portion to form an opening pattern in a processing container; In the container, plasma treatment is performed on a process gas containing a substance containing tritium, and the plasma is irradiated on the organic layer; and in the processing container, plasma is etched on the etching gas through the opening. Patterning and performing the etching operation on the etching target portion 02. The plasma processing method according to item 22 of the patent application scope, wherein the substance having Η is Η2. 2 4. The plasma processing method as described in item 22 of the scope of patent application, wherein the aforementioned substance having Η is NΗ3. 25. The plasma processing method as described in item 22 of the scope of the patent application, -84-(4) (4) 200401365, wherein the aforementioned processing gas system contains N2. 2 6. The plasma processing method as described in item 22 of the scope of patent application, wherein the organic layer is a cover layer. 27. The plasma processing method according to item 26 in the scope of the patent application, wherein the cover layer is a photoresist layer. 28. The plasma processing method according to item 27 in the scope of the patent application, wherein the photoresist layer is formed of an ArF photoresist or an F2 photoresist. 29. The plasma processing method according to item 22 of the scope of the patent application, wherein the processing gas and the etching gas system are the same gas. 30. The plasma processing method as described in item 22 of the scope of the patent application, wherein the etching gas system further adds a gas of other gas to the processing gas. 31. The plasma processing method according to item 22 of the scope of patent application, wherein the etching target portion is a Si02 layer. 3 2 · The plasma treatment method as described in item 31 of the scope of patent application, wherein 1 the aforementioned etching gas system contains a gas of c5F8. 3 3. The plasma treatment method as described in item 22 of the scope of the patent application, wherein the aforementioned plasma irradiation operation is performed under an atmosphere of a pressure of 13.3 Pa (100 mT0rr) or less. 3 4 The plasma treatment method described in item 33 of the scope of the patent application, wherein the aforementioned plasma irradiation operation is performed under an atmosphere having a pressure of I.1 to 4.0 Pa (8 \ 30 mTorr) or less. 35. A plasma treatment method, comprising: -85- (5) 200401365 On the surface, preparing an object to be processed having a photoresist layer composed of an ArF photoresist or F2 photoresist And, for the object to be processed, the operation of irradiating a plasma containing a processing gas having a substance of N to improve the plasma resistance of the photoresist layer. 36. The plasma treatment method according to item 35 of the scope of patent application, wherein the substance having N is N2. 37. The plasma treatment method described in item 35 of the scope of patent application ', wherein the substance having N is NH3. 38. The plasma processing method as described in item 35 of the scope of patent application, wherein the aforementioned processing gas system has a substance of tritium. 39. The plasma processing method as described in item 38 of the scope of patent application, wherein the substance having rhenium is one or more selected from H2, CHF3, CH2F2, and ch3f. 4 0.—A plasma treatment method, which is characterized by: An object to be processed having an etching target portion, an antireflection layer covering the etching target portion, and a photoresist layer composed of an ArF photoresist or an F2 photoresist to form an opening pattern covering the antireflection layer is disposed on The operation in the processing container; the operation of introducing a processing gas into the processing container; the operation of plasmaizing the processing gas; and applying the plasma to the object to be processed to improve the electrical resistance of the photoresist layer At the same time, the anti-reflection layer is engraved with the opening pattern and the anti-reflection layer. 4 1. The plasma processing method as described in item 40 of the scope of patent application, -86-(6) (6) 200401365, wherein the aforementioned processing gas system contains N2. 42. The plasma processing method as described in item 41 of the scope of patent application, wherein the sensor to be processed is placed in the processing container, and the plasma is applied to the object to be processed. The above operation is based on the aforementioned sensor, which supplies high-frequency power at frequencies above 100 MHz and high-frequency power at frequencies above 3 MHz. 4 3 · The plasma processing method described in item 42 of the scope of patent application, wherein the high-frequency power of the frequency of 3 MHz or more is 100 W or less. 44. The plasma processing method as described in item 41 of the scope of patent application, wherein the processing gas system is composed of H2. 45. A plasma processing method, comprising: in a processing container, arranging an etching target layer, an anti-reflection layer covering the etching target layer, and a mask layer covering the anti-reflection layer to form an opening pattern. The work of the object to be processed; the operation of introducing the processing gas containing H2 into the processing container »the operation of plasma processing the processing gas; and the opening pattern of the cover layer through the plasma , So that the anti-reflection layer is selectively etched to the mask layer. 46. The plasma processing method described in item 45 of the scope of patent application, wherein the sensor to be processed is placed in the processing container, and the etching operation is performed on the sensor. , Superimpose and apply high-frequency power above 100MHz and high-frequency power above 3MHz (7) 200401365 force. 47. The plasma processing method as described in item 46 of the scope of patent application, wherein the high-frequency power of the frequency above 3MHZ is below 100W. 4 8. The plasma processing method as described in item 45 of the scope of patent application, wherein the mask layer is an ArF photoresist layer or an F2 photoresist layer. 49. The plasma processing method as described in item 45 of the scope of patent application, wherein the aforementioned processing gas system is composed of H2. 50. The plasma processing method as described in item 49 of the scope of the patent application, further comprising: after the operation of etching the anti-reflection layer, plasmatizing CF 4 and Η 2 through the cover layer The opening pattern is used to etch the aforementioned layer to be etched, and the operation is continued until it is halfway; and, after the etching is performed to the way, the etching gas is plasmatized to etch the remaining layer of the etched layer. Ministry of Homework. 51. The plasma processing method as described in item 50 of the scope of patent application, wherein the mask layer is an ArF photoresist layer or an F2 photoresist layer. 5 2. The plasma processing method as described in item 50 of the scope of patent application, wherein the cover layer is made of methyl acrylic resin. 53. The plasma treatment method as described in item 50 of the scope of patent application, wherein the aforementioned etching gas system is different from other gases of CF4 and H2 mixed gas. 54. The plasma processing method according to item 50 of the scope of the patent application, wherein the age-targeted layer is the s i0 2 layer, and the etching gas system includes C 5 F 8 and O 2 gas. -88- (8) (8) 200401365 55. A plasma processing method, comprising: having an etching target layer and forming an opening pattern covering the etching target layer, and using an ArF photoresist or F2 light The object to be processed in the mask layer formed by the resist is placed on a mounting table; CF4 and H2 are plasmatized, and the object layer for engraving is etched through the opening pattern of the mask layer, An initial etching operation up to the middle; and a main etching operation for etching the aforementioned etching target layer by plasma-etching an etching gas containing fluorocarbon after the initial etching operation. 56. The plasma processing method according to item 55 in the scope of the patent application, wherein the etching target layer is a Si 02 layer. 5 7. A plasma treatment method, comprising: an acrylic resin mask having an etching target layer, an anti-reflection layer covering the etching target layer, and forming an opening pattern covering the anti-reflection layer. The object to be processed in the first layer is placed on a mounting table. The first etching operation is performed on plasma of cf4, and the etching of the anti-reflection layer is performed by the opening pattern of the cover layer. The slurry is etched through the opening pattern of the cover layer to the etching target layer, and the second etching operation is continued until midway: and after the second etching operation, the etching gas containing fluorocarbon is supplied. The third etching operation is performed by plasma to etch the uranium etching target layer. 58. The plasma processing method according to item 57 in the scope of the patent application, wherein the etching target layer is a Si 02 layer. 200401365 Ο) 59. A plasma processing method, comprising: a sensor disposed in a processing container, placing a layer having an axis-etched object layer and a mask layer covering the etching object layer to form an opening; The work of the object to be processed; the operation of introducing the processing gas containing H2 in the aforementioned processing container, the operation of supplying the above-mentioned sensor with a frequency of 1 ο 0 Μ Η Z or higher frequency power and a frequency of 3 ΜΗζ or higher frequency power; And, the operation for reducing the pressure in the processing container to 13.3 Pa (100 mTorr) or less " 60. The plasma processing method as described in item 59 of the patent application scope, wherein the high-frequency power of the frequency above 3 MHz is i 〇〇W or less. 61. A plasma processing method, comprising: processing a mask layer having an etching target portion and forming an opening pattern covering the etching target portion and comprising an ArF photoresist or an F2 photoresist; The operation of placing in a processing container; the operation of plasma-treating a processing gas containing a substance containing N in the processing container and irradiating the photoresist layer; and the etching in the processing container. Plasma is formed by gas, and etching is performed on the etching target portion through the opening pattern. 62. The plasma processing method as described in item 61 of the scope of patent application, wherein the substance having N is N2. 63. The plasma processing method as described in item 62 of the scope of the patent application, -90- (10) (10) 200401365, wherein the aforementioned processing gas system includes h2. 64. The plasma processing method according to item 62 of the scope of the patent application, wherein the processing gas system includes one or more selected from the group consisting of CHF3 'CH2F2' CH3F. 65. The plasma processing method according to item 61 of the scope of patent application, wherein the substance having N is NH3. 66_—A plasma processing method, comprising: having an etching target portion, an antireflection layer covering the etching target portion, and forming an opening pattern covering the antireflection layer, and using ArF photoresist or F 2 light A photoresist layer composed of a resist is disposed in a processing container. In the foregoing processing container, plasma is formed for a processing gas containing a substance having N. The above-mentioned opening pattern is used for the foregoing. The anti-reflection layer performs a first etching operation for etching; and a second etching operation for etching the etching target portion through the opening pattern in the processing container by plasma-etching the etching gas. 67. The plasma processing method according to item 6 of the scope of patent application, wherein the substance having N is N2. 68. The plasma processing method as described in item 67 of the scope of patent application, wherein the processing gas system contains H2. 69. The plasma processing method described in item 68 of the scope of the patent application, wherein the aforementioned first etching operation is performed so that the pressure in the aforementioned processing container becomes 107 to 160 Pa (800 to 1200 mTorr). (11) (11) 200401365 70. The plasma processing method as described in item 69 of the scope of the patent application, wherein 'the said etching target layer is the Si 0 2 layer', and the aforementioned etching gas system contains a gas of C5F8. 7 1 · The plasma treatment method as described in item 70 of the scope of the patent application, wherein the aforementioned C5F8 is 1,1,1,4,4,5,5,5 -octafluoro- 2-pentyne. 72. The plasma processing method according to item 67 of the scope of the patent application, wherein the aforementioned processing gas system includes one or more selected from the group consisting of CHF3, CH2F2, and CH3F. 73. The plasma processing method according to item 6 of the scope of the patent application, wherein the substance having N is NH3. 74. The plasma processing method according to item 66 of the scope of the patent application, wherein the etching target layer is a Si02 layer, and the etching gas system contains a gas of C4F6. 75. The plasma processing method according to item 66 of the scope of application for a patent, wherein said etching target layer is a Si 02 layer, and said etching gas system contains a gas of c5f8. 7 6 • The plasma processing method described in item 75 of the scope of patent application, wherein the aforementioned CsFs is a linear CSF8. 77. The plasma processing method as described in item 76 of the scope of patent application, wherein the aforementioned linear C5F8 series 1 is :! , I, 4,4,5,5,5-octafluoro-2-pentamidine. * 78. The plasma treatment method as described in item 75 of the patent application scope, wherein 'the processing gas system package a Ν2 and η2, the aforementioned 10th engraving operation -92- (12) (12 200401365 is implemented by setting the pressure in the processing container to 107 to 160 Pa (800 to 1200 mTorr). 79. A plasma processing method, comprising: arranging an object to be processed having an etching target layer and an organic cover curtain layer forming an opening pattern covering the aforementioned feeding target layer, and being arranged to expose a substance containing Si Work in a processing container constituting a component; introducing into the processing container at least one type of processing gas selected from the group consisting of H2, N2, and He; and performing electricity on the processing gas Plasma is a plasma treatment of the organic cover layer. 80. The plasma processing method as described in item 79 of the scope of application for a patent, wherein after the plasma processing operation, a uranium engraving operation is performed on the etching target layer. 81. The plasma processing method according to item 79 in the scope of the patent application, wherein the organic cover layer is an organic photoresist layer. 82. The plasma processing method described in item 81 of the scope of the patent application, wherein the aforementioned organic photoresist layer in Langzhong is composed of an ArF photoresist or an f2 photoresist. 8 3 · The plasma processing method as described in item 79 of the scope of the patent application, wherein the aforementioned substance containing S i is composed of a single crystal S i. 84. The plasma processing method according to item 79 of the scope of the patent application, wherein the substance containing Si is composed of SiC. 8 5. The plasma processing method described in item 79 of the scope of the patent application, wherein the aforementioned constituent member having an exposed portion containing Si is provided -93-(13) (13) 200401365 in the aforementioned processing container. Opposite electrode of the object to be processed. 86. A plasma processing method, comprising: disposing an object to be treated having an etching target layer, an organic film covering the foregoing etching target layer, and an organic cover curtain layer forming an opening pattern covering the organic film; Operation in a processing container having a constituent member containing a substance exposed portion containing Si; operation of introducing an etching gas into the processing container; plasma forming the etching gas, and using the opening pattern of the organic cover Etching the organic film; introducing at least one processing gas selected from the group consisting of 112′1 ^ 2 and He into the processing container; and performing electricity on the processing gas Plasma is a plasma treatment of the organic cover layer. 87. The plasma processing method according to item 86 of the scope of the patent application, wherein the etching gas system includes C F4. 8 8 · The plasma processing method according to item 86 of the scope of application for a patent, wherein after the plasma processing operation, the plasma etching process is further performed. 89. The plasma processing method according to item 86 in the scope of the patent application, wherein the organic film is an organic reflection prevention film. 9 〇 The plasma processing method according to item 86 of the scope of the patent application, wherein the organic mask layer is an organic photoresist layer. 91. The plasma processing method according to item 90 of the scope of the patent application, wherein the organic photoresist layer is composed of ArF photoresist or F2 photoresist -94- (14) (14) 200401365. 92. The plasma processing method according to item 86 of the scope of the patent application, wherein the substance containing S i is composed of a single crystal S i. 93. The plasma processing method according to item 86 of the scope of patent application, wherein the substance containing Si is made of SiC. 94. The plasma processing method according to item 86 of the scope of patent application, wherein the aforementioned constituent member having an exposed portion containing a substance of Si is a counter electrode of a processing object provided in the aforementioned processing container. 95. A plasma processing method, comprising: disposing an organic film having an etching target layer covering the aforementioned etching target layer and an organic cover screen layer forming an opening pattern covering the aforementioned organic film; Operations in a processing container having a constituent member containing a substance exposed portion of Si; operation of introducing 112 into the processing container; and plasmaizing the introduced H2 through the opening pattern of the organic cover curtain layer The organic film is etched. 9 6. The plasma processing method according to item 95 of the scope of application for a patent, wherein after the operation of etching the organic film, the method further includes an operation of etching the object layer to be etched. 97. The plasma processing method according to item 95 of the scope of application for a patent, wherein the organic film is an organic reflection prevention film. 98. The plasma processing method according to item 95 of the scope of application for a patent, wherein the organic cover layer is an organic photoresist layer. 9 9 · According to the plasma treatment method described in item 98 of the scope of application for patent, -95- (15) (15) 200401365, wherein the organic photoresist layer is composed of ArF photoresist or F2 photoresist . 100. The plasma processing method according to item 95 of the scope of application for a patent, wherein the substance containing S i is composed of a single crystal S i. 101. The plasma processing method as described in item 95 of the scope of patent application, wherein the substance containing Si is composed of SiC. 1 02. The plasma processing method according to item 95 in the scope of the patent application, wherein the aforementioned constituent member having the substance exposed portion including Si is a counter electrode of the object to be processed disposed in the processing container. 103. A plasma processing method, comprising: a quilt having an etching target layer and a photoresist layer composed of an ArF photoresist or an F2 photoresist to form an opening pattern covering the etching target layer. A process in which a processing body is disposed in a processing container; a process in which a processing gas containing C2f4 is introduced into the processing container in which the object to be processed is stored; a process in which the processing gas is plasmatized; and Plasma, so that the worm-engraved object layer in the object to be processed can be engraved by the opening pattern of the photoresist layer. 104. The plasma processing method as described in item 103 of the scope of patent application, 'wherein' the aforementioned etching target layer is a carbon-containing layer. 105. The plasma processing method as described in the scope of the patent application item No. 03, wherein the aforementioned etching target layer is an organic layer. 106. A plasma processing method, comprising: -96- (16) (16) 200401365 A structure to be treated having an etching target layer and a mask layer forming an opening pattern covering the etching target layer is arranged. Operation in a processing container; Operation in which a processing gas containing c2f4 and 〇2 is introduced into the processing container containing the object to be processed; operation of plasmatizing the processing gas; and using the processing gas Plasma enables the etching target layer in the object to be etched through the opening pattern of the mask layer. 107. The plasma processing method as described in item 106 of the scope of the patent application, wherein the mask layer is a photoresist layer. 108. The plasma processing method according to item 107 of the scope of patent application, wherein the etching target layer is an anti-reflection layer. 109. The plasma processing method according to item 107 in the scope of the patent application, wherein the aforementioned photoresist layer is made of an ArF photoresist or an f2 photoresist. Η 0. The plasma processing method according to item 106 of the scope of patent application, wherein the etching target layer is a carbon-containing layer. 1 1 1 · The plasma processing method according to item 106 of the scope of patent application, wherein the above-mentioned layer to be touched is an organic layer. 1 1 2-A plasma processing method, comprising: an ArF photoresist or an anti-reflection layer having an etched portion, an anti-reflection layer covering the etched portion, and an opening pattern covering the anti-reflection layer. F2 photoresist layer of the photoresist layer of the object to be disposed in the processing container; -97- (17) (17) 200401365 In the foregoing processing container, for the substances containing c and F and An operation of plasma etching with an erbium substance, and etching the anti-reflection layer through the opening pattern; and etching the object to be etched. 1 1 3 · The plasma processing method described in item 112 of the scope of patent application ′, wherein the substance having rhenium is hydrogen carbon. 1 1 4. The plasma treatment method described in item 1 of the scope of application for patent] 3, wherein the aforementioned hydrogen-carbon type CH4. 1 1 5. The plasma processing method described in item 丨 丨 2 of the scope of patent application ′, wherein the aforementioned substance having Η is H2. 1 1 6. The plasma treatment method described in item 丨 丨 2 of the scope of the patent application ′ wherein the aforementioned substance having Η is a hydrofluorocarbon. 1 17. The plasma treatment method described in item 116 of the scope of the patent application, wherein the ratio of the number of the above-mentioned hydrofluorocarbon-based fluorene atoms to the number of F atoms 値 is 3 or more. 1 1 8 · The plasma treatment method described in item η 7 of the scope of patent application ′, wherein the aforementioned HFC is CH3F. 1 1 9. The plasma treatment method described in item 8 of the scope of the patent application 'wherein' The ratio of the aforementioned CH3F flow rate in the aforementioned etching gas to the aforementioned substance flow rate having C and F is ·· 〇4〜 0.07. 1 2. The plasma processing method described in item 112 of the scope of the patent application ′ wherein ‘the substance having C and F is CF4. 121. A plasma processing method, comprising: an anti-reflection layer -98- (18) (18) 200401365 having an M-engraved object portion and covering the etching object portion, and forming an opening covering the anti-reflection layer The work of arranging a patterned cover layer in a processing container: Plasma plasma of an etching gas containing substances having C and F and hydrogen and carbon, and etch through the opening pattern. The operation of the antireflection layer; and the operation of etching the etching target portion. 1 2 2 The electric award processing method described in item 121 of the scope of patent application, wherein the aforementioned hydrogen-carbon type CH4. 1 2 3. The plasma treatment method described in item 121 of the scope of patent application, wherein the substance having C and F is CF4. 1 2 4 · The plasma processing method according to item 121 of the scope of the patent application, wherein the mask layer is an ArF photoresist layer or an F2 photoresist layer. 125 · —A plasma processing method, comprising: arranging an object to be treated having an etching target portion, an antireflection layer covering the etching target portion, and a mask layer forming an opening pattern covering the antireflection layer; Operations in a processing vessel; In the aforementioned processing vessel, uranium-engraved gas containing a substance having C and F and a substance having C, plutonium, and F and a ratio of plutonium atoms to F atomic ratios of 3 or more An operation of plasma-etching the anti-reflection layer through the opening pattern; and an operation of touching the etching target portion. 126. The plasma processing method according to item 125 of the scope of application, wherein the substance having C, C, and F and the ratio of the number of Η atoms to the number of F atoms is 値 3 or more is CH3F. -99- (19) (19) 200401365 1 2 7. The plasma processing method as described in item No. 125 of the patent application scope, wherein the aforementioned substance having C and F is CF4. 1 2 8 · The plasma processing method described in item 1 27 of the scope of patent application, wherein the ratio of the flow rate of the CH3F to the flow rate of the substance having C and F in the etching gas is 0.0 4 to 0. 0 7. 1 2 9 · The plasma processing method as described in item 125 of the scope of patent application, wherein the mask layer is an ArF photoresist layer or an F2 photoresist layer. 13〇 • A plasma processing method, comprising: a cover having an etching target portion and a photoresist layer composed of an ArF photoresist or an F2 photoresist, and an opening pattern covering the etching target portion. A process in which a processing body is disposed in a processing container; a process in which a processing gas containing a substance having C and F and CO is plasmatized, and the plasma is irradiated onto the photoresist layer; And, in the processing container, the etching gas is plasmatized, and the plasma is used to etch the etching target portion through the opening pattern. 1 3 1. The plasma processing method as described in item 130 of the scope of patent application, wherein the substance having C and F is CF4. 1 2 2. The plasma processing method as described in item 130 of the scope of the patent application, wherein the aforementioned processing gas and the aforementioned gas system are the same gas. 133. The plasma processing method according to item 132 of the scope of patent application, wherein the etching target portion is an antireflection layer. 134. — A plasma processing method, comprising: -100- (20) (20) 200401365 having an etching target portion, an anti-reflection layer covering the etching target portion, and forming an opening pattern covering the anti-reflection layer. The photoresist layer composed of an ArF photoresist or F2 photoresist is disposed in a processing container. In the aforementioned processing container, the first component containing a substance having C and F and CO is included. A first etching operation for performing plasma etching with an etching gas, and through the opening pattern through the opening pattern to perform etching on the antireflection layer; and in the processing container, electrically performing a second etching gas. The slurry is passed through the opening pattern through the plasma, and the second etching operation is performed on the etching target portion. 1 3 5 · The plasma treatment method described in item 134 of the scope of patent application, wherein the substance having C and F is CF4. 136. The plasma processing method according to item 134 in the scope of the patent application, wherein the etching target portion is a layer of Si02, and the second etching gas includes C5F8. 1 3 7 · The plasma processing method according to item 134 of the scope of the patent application, wherein the etching target part is a layer of Si 0 2 and the second etching gas is a gas containing c4F6. 1 3 8 · A plasma processing method, comprising: an object to be treated having an etching target portion, an antireflection layer covering the etching target portion, and a mask layer forming a cover pattern covering the opening pattern of the antireflection layer, The operation arranged in the processing container; In the foregoing processing container, the first etching -101-(21) (21) 200401365 gas containing CF4 and CO is plasmatized, and the plasma is transmitted through the opening pattern through the plasma. The first etching operation is performed on the anti-reflection layer; and in the processing container, the second uranium-etched gas is plasmatized, and the plasma is transmitted through the opening pattern, and the first The second etching operation for etching is performed on the object to be etched. 1 3 9 • The plasma processing method described in item 138 of the scope of patent application, wherein the above-mentioned saturated object portion is a layer of Si 0, and the second etching gas system includes C 4 F 6 ° 1 4 0 The plasma processing method according to item 139 in the scope of the patent application, wherein the etching target portion is a SiO 2 layer, and the second etching gas system includes a C5Fs gas. 141. A plasma processing method, comprising: arf photoresist or F2 having an etching target layer, an organic reflection preventing layer covering the etching target layer, and forming an opening pattern covering the organic reflection preventing layer. A photoresist layer composed of a photoresist layer, the object to be processed is disposed in a processing container; the processing container is introduced with an etching gas containing a substance containing Si; and the etching gas is electrically charged. The slurry is etched through the pattern of the photoresist layer to etch the organic reflection prevention layer. W2. The plasma processing method according to item 141 of the scope of patent application, wherein the substance containing Si is SiF4. 1 43-The plasma processing method as described in claim No. 142 of the patent application range, wherein the etching gas system contains CHF3. -102- (22) (22) 200401365 14 4. The plasma processing method according to item 142 of the scope of patent application, wherein the aforementioned etching gas system contains ΗB r. 1 45. The plasma processing method according to item 42 of the scope of patent application, wherein the etching gas system contains He. 14 6. The plasma processing method according to item 142 of the scope of application for a patent, wherein the etching gas system contains H2. 1 47. The plasma processing method according to item 141 of the scope of patent application, wherein after the operation of etching the organic reflection prevention layer, the method further comprises: passing the opening pattern of the ArF photoresist layer to the foregoing The target layer is etched to perform plasma etching. 148. A plasma processing method, comprising: a sensor positioned in a processing container; and a substrate to be processed having an etching target layer and a cover layer covering the etching target layer to form an opening. As an etiir dish, in the processing container, at least a part of the object to be processed and the surface thereof becomes Si, the operation of introducing an inert gas into the processing container; at least a part of the inert gas will be ionized. The operation of applying high-frequency energy to the aforementioned processing container; the operation of introducing an etching gas into the aforementioned processing container; the operation of plasma-forming the etching gas; and, In the processing container, an etching operation is performed on the etching target layer through the opening pattern of the cover layer. -103- (23) (23) 200401365 1 4 9 · The plasma processing method described in item No. 148 of the scope of application for a patent, wherein the aforementioned cover layer is an A r F photoresist layer or F 2 light Resistor layer. 15 0 · The plasma processing method according to item 148 in the scope of patent application, wherein at least a part of the aforementioned surface becomes a focusing ring of the component system of S i located around the object to be processed. 1 51. The plasma processing method according to item 148 in the scope of the patent application, wherein at least a part of the surface becomes a component of Si, and the etching gas is introduced into the shower head in the processing container. 1 5 2. The plasma processing method according to item 148 in the scope of the patent application, wherein the etching target layer is Si oxide, and the etching gas system includes C4F6, < 3 Khan 8 and C5FS. Group of at least one. I 5 3. The plasma processing method described in item No. 148 of the scope of patent application, wherein '' has a plasma removing operation for the mask layer in multiple stages after the aforementioned etching operation. 1 5 4 · The plasma treatment method described in item 153 of the scope of the patent application, wherein the above-mentioned plasma removal of the cover layer in multiple stages is performed by: A first removal operation for removing a part of the cover layer by plasma and a second removal operation for removing at least a portion of the cover layer remaining in the first removal operation by a plasma of a gas not containing a fluorine compound. 155. The plasma treatment method according to item 154 of the patent application scope, wherein the cover layer is an ArF photoresist layer, and the gas system C F 4 used in the above-mentioned removal operation. -104- (24) (24) 200401365 1 5 6. The plasma processing method described in item 4 of the scope of patent application] 48, wherein the aforementioned operation of introducing energy into the aforementioned processing container is included in the The antenna outside the processing container is used to apply high-frequency power. 1 5 7 According to the plasma processing method described in item No. 丨 4 of the scope of the patent application, wherein the aforementioned operation of introducing energy into the aforementioned processing container is the object of the aforementioned sensor provided in the aforementioned processing container. Electrode to apply high-frequency power. 158. An electric paddle processing method, comprising: a sensor positioned in a processing container; and a processed object having an etching target layer and a mask layer covering the etching target layer to form an opening pattern. The operation of forming an Si-containing layer on the surface of the cover layer in the processing container; the operation of introducing an etching gas in the processing container; the operation of plasma forming the etching gas; and In the processing container, the plasma of the etching gas is used to perform the etching operation on the etching target layer through the opening pattern of the mask layer. 159. The plasma processing method as described in item 58 of the scope of application for a patent, wherein after the plasma etching operation described above, there is a plasma removal operation for the cover layer in multiple stages. 160. The plasma treatment method described in the scope of application patent No. 159, wherein the aforementioned operation of removing the plasma layer for the cover layer in multiple stages includes removing by a plasma of a gas containing a fluorine compound. Mask layer -105- (25) (25) 200401365 Part of the first removal operation and at least part of the second removal of the mask layer remaining in the first removal operation by the electric award of a gas that does not contain a fluorine compound operation. ] 6 1. The plasma treatment method described in item 60 of the patent application 'wherein' the aforementioned cover layer is an ArF photoresist layer or an F2 photoresist layer, and the gas used in the aforementioned first removal operation Department of CF4. 162. The plasma processing method as described in item 158 of the scope of the patent application, wherein the aforementioned mask layer is an ArF photoresist layer or an F2 photoresist layer. 163. The plasma processing method according to item 158 of the scope of the patent application, wherein the etching target layer is Si oxide, and the etching gas system includes at least one selected from C4F6, c4f8, and C5FS. 1 64. The plasma treatment method described in item 158 of the scope of patent application, wherein the aforementioned operation of forming the Si-containing layer is performed by the PVD method. 065. If the scope of patent application is 158 The plasma processing method described in the above item, wherein the operation of forming the Si-containing layer is carried out by a CVD method. A plasma processing method is characterized in that: it is provided that at least a part of the surface is provided in the interior to be S The operation of the member i, the first electrode, and the processing container of the second electrode located at the position facing the first electrode; The first electrode 'placed in the processing container has an etching target layer and -106- (26) 200401365 Covering the object to be etched to form an opening pattern of the object to be processed: Introducing an inert gas into the processing container: Applying high-frequency power to the first electrode Operation: The operation of applying high-frequency power to the second electrode; the operation of introducing an etching gas into the processing container; the etching of the processing container by using the high-frequency power Gas, and, for the moment the target layer is etched through the opening operation of the cover layer is patterned screen. 167. The plasma processing unit described in item 166 of the scope of patent application, wherein at least a part of the aforementioned surface becomes an electrode plate of the front electrode of the component of Si. 168. The plasma processing unit described in item 166 of the scope of application for a patent, wherein after the aforementioned plasma etching operation, there is also a multi-stage masking operation to remove the plasma. 16 9. A plasma processing method, comprising: a sensor positioned in a processing container, having an opening pattern formed by etching and covering the etching target layer, and formed by an ArF light F2 photoresist The operation of the object to be processed constituted by the photoresist layer; the operation of introducing an etching containing a Si compound into the aforementioned processing container; the operation of plasma forming the aforementioned etching gas; and the aforementioned processing container using the aforementioned The opening pattern of the aforementioned photoresist layer in the plasma of the etching gas, and the etching of the aforementioned etching target layer. 170. According to the plasma treatment described in item 169 of the scope of the patent application and the second method of the above-mentioned etching method, the method of using the target layer resist or etching gas is carried out -107- (27) 200401365 Among them, the aforementioned Si compound is Si F 4. • 108-