JP2008252139A - Dry etching method for interlayer insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a high etching precision by suppressing the generation of a striation in the case of dry-etching the interlayer insulating film covered with a resist mask formed by the ArF photolithography. <P>SOLUTION: In the case of fine processing of holes and trenches by dry etching in a plasma environment, fluorocarbon compound gas is employed for an etching gas which is a halogen group gas (halogen elements are F, I and Br) wherein at least one of the I and Br is 26% or below of the total amount of halogen in terms of an atomic composition ratio and the remaining material is F; however, a fluorocarbon compound gas excluding CF<SB>3</SB>Br, C<SB>2</SB>F<SB>5</SB>Br, C<SB>3</SB>F<SB>7</SB>Br and C<SB>3</SB>F<SB>6</SB>Br<SB>2</SB>is used. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for dry etching an interlayer insulating film, and more particularly, to an interlayer insulating film for finely processing holes and trenches by dry etching an interlayer insulating film covered with a resist mask formed using ArF photolithography. The present invention relates to a dry etching method.

In recent years, along with higher integration and higher speed of LSI, semiconductor elements have been miniaturized and multilayered. As a photolithography method in this case, as represented by an ArF photolithography method, a method using a laser having a short wavelength (for example, an excimer laser) is used, and a resist mask is formed by fine patterning. When the interlayer insulating film covered with such a resist mask is dry-etched to finely process wiring holes, trenches, etc., high processing accuracy is required to obtain a uniform etching shape in the depth direction. ing. In this case, it is known to perform etching by introducing a predetermined etching gas in a plasma atmosphere in order to increase anisotropy (Patent Document 1).

  By the way, as a resist material used in the ArF photolithography method, it has been proposed to use a resist material composed of a compound having no benzene ring in order to provide sensitivity in the vacuum ultraviolet region (Non-patent Document 1). In the case of this type of resist material, if fine patterning is performed using a laser having a short wavelength, the resist mask becomes weak accordingly, and the plasma resistance is lower than that used in other photolithography methods. .

  For this reason, when etching is performed in a plasma atmosphere, damage is caused by exposure to plasma, and edge roughness occurs in the edge portion of the patterned region of the resist mask (the shape of the resist mask is deformed). If etching is continued in such a state, there is a problem that the shape is transferred to holes and trenches to be formed in the interlayer insulating film, causing striations. In this case, the requirement for high etching processing accuracy cannot be satisfied.

In order to solve such a problem, a mixed gas containing a fluorocarbon gas was used, and this mixed gas was introduced in a low-pressure plasma atmosphere, and was covered with a resist mask formed using an ArF photolithography method. It has been proposed to dry-etch the interlayer insulating film (Patent Document 2).
Japanese Patent Laid-Open No. 11-31678 (see, for example, claims) Japanese Patent Application No. 2004-56962 (for example, refer to the description of claims) Koji Nozaki and Ei Yano, FUJITSU Sei.Tech.J., 38,1 P3-12 (June 2002)

  However, if a predetermined mixed gas is introduced at a low pressure and dry etching is performed, generation of striation can be suppressed and high etching accuracy can be obtained, but stable discharge can be obtained under a pressure lower than a predetermined pressure (for example, 0.133 Pa). The etching apparatus that can be used is limited, and the versatility is poor.

  In view of the above, an object of the present invention is to provide a dry etching method for an interlayer insulating film that can suppress the occurrence of striations and obtain high etching processing accuracy.

In order to solve the above-described problems, an interlayer insulating film dry etching method of the present invention is a plasma etching method in which an interlayer insulating film covered with a resist mask formed using ArF photolithography is introduced into a predetermined etching gas. In a dry etching method of an interlayer insulating film in which holes and trenches are finely processed by dry etching in an atmosphere, the etching gas is a halogen-based gas (halogen is F, I, Br), and at least one of I and Br One is a fluorocarbon compound gas having an atomic composition ratio of 26% or less of the total amount of halogen and the remainder being F , provided that CF ₃ Br, C ₂ F ₅ Br, C ₃ F ₇ Br, and C It is characterized by using a fluorocarbon compound gas excluding ₃ F ₆ Br ₂ .

  According to the present invention, an etching gas is formed by using a fluorocarbon compound gas containing at least one of I and Br, which forms a stable compound and functions as an etchant for Si itself, as an etching gas. Without depending on the pressure, the F atom number density in the plasma atmosphere can be reduced to reduce damage to the resist mask, and the occurrence of striation can be suppressed. In this case, if at least one of I and Br is contained in an atomic composition ratio exceeding 26% of the total amount of halogen, there are problems such as a decrease in etching rate and inability to perform etching in a desired shape.

The fluorocarbon compound gas is an iodinated fluorocarbon compound gas and a brominated fluorocarbon compound gas excluding CF ₃ Br, C ₂ F ₅ Br, C ₃ F ₇ Br, and C ₃ F ₆ Br ₂ . Either one or a mixed gas thereof is preferable.

In this case, the iodinated fluorocarbon compound gas is at least one selected from CF ₃ I, C ₂ F ₅ I, C ₃ F ₇ I, and C ₃ F ₆ I ₂ , or the iodinated fluorinated gas. What is necessary is just to set it as the mixed gas containing 2 or more types selected from carbon compound gas and HI or HBr.

The brominated fluorocarbon compound gas may be at least one selected from CF ₃ Br, C ₂ F ₅ Br, C ₃ F ₇ Br, and C ₃ F ₆ Br ₂ , or the brominated fluorocarbon. What is necessary is just to set it as the mixed gas containing 2 or more types selected from compound gas and HI or HBr.

The etching gas may be a mixed gas of CF ₄ and C ₂ F ₄ I ₂ or C ₂ F ₄ Br ₂ .

  The etching gas may be a mixed gas of at least one of HI and HBr and a fluorocarbon compound.

The etching gas may be a mixed gas of CF ₃ I and a fluorocarbon compound.

The etching gas may be a mixed gas of CF ₃ Br and a fluorocarbon compound.

  Here, in order to prevent the etched holes and trenches from being filled by adjusting the deposition amount of the reaction product by etching, the etching gas is used in an amount of 3 to 15 with respect to the total flow rate of the etching gas. Oxygen should be added in the range of%. In this case, if it is less than 3%, the above effect cannot be achieved, and the amount of deposition cannot be adjusted. On the other hand, if it exceeds 15%, the ArF resist is damaged and etched.

  As described above, the dry etching method for an interlayer insulating film according to the present invention has an effect of suppressing the occurrence of striation and obtaining high etching processing accuracy.

  Referring to FIG. 1, reference numeral 1 denotes an etching apparatus for finely processing wiring holes, trenches and the like by dry etching the interlayer insulating film of the present invention. The etching apparatus 1 uses discharge plasma (NLD plasma) generated in an area including zero magnetic field, and has a chamber 11 provided with a vacuum exhaust means 12 such as a dry pump, a rotary pump, or a turbo molecular pump.

  The chamber 11 is composed of an upper plasma generation chamber 11a and a lower substrate processing chamber 11b formed by a cylindrical side wall 13 made of a dielectric material such as quartz. Three magnetic field coils 14, 15 and 16 are provided outside the cylindrical side wall 13 at predetermined intervals to constitute a magnetic field generating means. The three magnetic field coils 14, 15 and 16 are attached to a yoke member 17 made of a high magnetic permeability material so as to surround the outside from above and below. In this case, a current in the same direction is supplied to the upper and lower magnetic field coils 14 and 16, and a current in the opposite direction is supplied to the intermediate coil 15. Thereby, the position of the magnetic field zero continuous inside the cylindrical side wall 13 near the level of the intermediate coil 15 is formed, and an annular magnetic neutral line is formed.

  The size of the annular magnetic neutral line can be set as appropriate by changing the ratio of the current flowing through the upper and lower coils 14 and 16 and the current flowing through the intermediate coil 15. The position of can be appropriately set by the ratio of the currents flowing through the upper and lower magnetic field coils 14 and 16. Further, when the current flowing through the intermediate coil 15 is increased, the diameter of the annular magnetic neutral wire is reduced, and at the same time, the gradient of the magnetic field at the position of the magnetic field zero becomes gentle. An antenna 18 for generating a high-frequency electric field is provided between the intermediate coil 15 and the cylindrical side wall 13 and connected to a high-frequency power source 19 to constitute a magnetic field generating means. Then, NLD plasma is generated along the annular magnetic neutral line formed by the three magnetic field coils 14, 15 and 16.

  A substrate electrode 20 having a circular cross section, which is a substrate mounting portion on which the processing substrate S is mounted, is provided via an insulator 20a in the substrate processing chamber 11b so as to face the surface formed by the annular magnetic neutral line. Yes. The substrate electrode 20 is connected to the second high-frequency power source 22 via the capacitor 21 and becomes a floating electrode in terms of potential and has a negative bias potential.

  Further, the top plate 23 that partitions the plasma generation chamber 11a is hermetically fixed to the upper part of the cylindrical side wall, and is in a floating state in potential and forms a counter electrode. A gas introduction means 24 for introducing an etching gas into the chamber 11 is provided on the inner surface of the top plate, and the gas introduction means 24 is connected to a gas source via a gas flow rate control means (not shown). Yes.

As the interlayer insulating film in which wiring holes and trenches are finely processed using the etching apparatus 1, an oxide film such as SiO ₂ , a SiOCH material formed by spin coating such as HSQ or MSQ, or It is a low-k material having a relative dielectric constant of 1.5 to 3.0, which is a SiOC material formed by CVD, and includes a porous material.

  Examples of the SiOCH-based material include a trade name NCS / catalyst chemical industry, trade name LKD5109r5 / JSR, trade name HSG-7000 / Hitachi Chemical Co., trade name HOSP / Honeywell Electric Materials, trade name Nanoglass. / Honeywell Electric Materials, trade name OCD T-12 / Tokyo Ohka, trade name OCD T-32 / Tokyo Ohka, trade name IPS 2.4 / Catalyst Kasei Kogyo, trade name IPS 2.2 / Catalyst There are a product made by Kasei Kogyo Co., Ltd., brand name ALCAP-S5100 / Asahi Kasei Co., Ltd., brand name ISM / ULVAC, etc.

  Examples of the SiOC material include trade name Aurola 2.7 / Japan ASM Co., trade name Aurola 2.4 / Japan ASM Co., trade name Orion 2.7 / TRIKON, trade name Coral / Novellf, trade name Black Diamond / AMAT and others. Also, trade name SiLK / Dow Chemical, trade name Porous-SiLK / Dow Chemical, trade name FLARE / Honeywell Electric Materials, trade name Porous FLARE / Honeywell Electric Materials, trade name GX-3P / Honeywell It may be an organic low dielectric constant interlayer insulating film such as that manufactured by Electric Materials.

  On the interlayer insulating film, a resist mask is formed by predetermined patterning using photolithography in order to finely process wiring holes and trenches in the interlayer insulating film. As a photolithography method, an ArF photolithography method is used in order to cope with the miniaturization and multilayering of semiconductor elements accompanying the high integration and high speed of LSI. As a resist material for ArF photolithography, for example, there is a UV-6 / Shipley product for vacuum ultraviolet light.

  By the way, the resist material used in the ArF photolithography method may be composed of a compound that does not have a benzene ring in order to provide sensitivity in the vacuum ultraviolet region. When this type of resist material is subjected to fine patterning using a laser having a short wavelength, the resist mask becomes weak accordingly, and the plasma resistance is lower than those used in other photolithography methods.

Here, a conventional dry etching method for an interlayer insulating film, that is, for example, using an inductively coupled (ICP plasma) etching apparatus (not shown) and containing fluorocarbon gas (CxFy) under an operating pressure of 1 to 3 Pa. When an etching gas is introduced in a plasma atmosphere to perform etching (in this case, the Ar plasma density is ˜1 × 10 ¹¹ cm ⁻³ ), as shown in FIG. Due to the damage, edge roughness 33 occurs at the edge portion 32 of the patterned region of the resist mask 31 (the shape of the resist mask 31 is deformed). If the etching is continued in such a state, the shape is transferred to the holes and trenches 35 to be formed in the interlayer insulating film 34 and the striation 36 is generated, and the requirement for high etching processing accuracy cannot be satisfied.

  The occurrence of the above-described striation 36 is generally recognized as damage caused by ions during etching in a plasma atmosphere. Based on such recognition, even when the interlayer insulating film is etched by the NLD plasma etching apparatus 1 which is a low-pressure and high-density plasma, striations are considered to occur for the following reasons.

That is, in the NLD plasma etching apparatus 1, the output of the high-frequency power source 19 connected to the antenna 18 is normally 1 to 1.5 kW and the second high-frequency power source under an etching pressure of 0.3 to 0.7 Pa. The output (bias power) of 22 is set to 0.2 to 0.6 kW, and the Ar plasma density at this time is ˜1 × 10 ¹¹ cm ⁻³ . In this case, since the operating pressure is set lower than that of the conventional method, the plasma density is reduced. However, since the etching apparatus 1 is an efficient annular magnetic neutral discharge plasma, the amount of decrease in the plasma density is small.

  For this reason, the ion current density in the etching apparatus 1 is almost the same as that of the ICP plasma etching apparatus in which the occurrence of striation cannot be suppressed, and the output of the second high-frequency power source 22 is set to 0.3 KW. The ion energy is ˜1 KeV, and high energy ions collide with the resist mask 31. Therefore, when the interlayer insulating film is etched by the NLD plasma etching apparatus 1, it is considered that striation occurs.

By the way, even when an ICP plasma etching apparatus is used, it has been found that the occurrence of striation can be suppressed by setting the operating pressure to a predetermined value. This is because the physical quantity of neutral decomposition species (atoms, molecules, radicals) is reduced by setting the operating pressure low. In this case, decomposition species generated by decomposing CxFy gas include F, CF, CF ₂ , CF _3, etc. Among them, molecular radicals mainly function as polymerization precursors, but resist mask 31 The action as an etching substance is low. For this reason, the F atom having high reactivity with the organic substance reacts with the C═O group and other functional groups of the resist mask 31 to make the resist mask 31 more brittle. Therefore, the resist mask 31 is weakened by a radical reaction.

On the other hand, in dry etching of a porous low-k film, using C ₃ F ₇ I as an etching gas and under low-pressure and high-density plasma etching conditions, the etching rate of the resist mask decreases and the resist selectivity ratio increases. An improving phenomenon has been found. The reason why the etching rate of the resist mask is reduced is that the F radical, which is an etchant of the resist mask, reacts with I in the gas phase to form IF ₃ , IF ₅ , IF _{7 and the} like.

  In view of what has been described above, it is possible to suppress the occurrence of resist mask striation by using an ICP plasma etching apparatus and setting the operating pressure low. Among the radical species, the F atom density which is an etchant of the resist This is because of the decrease in When a gas containing iodine atoms is used, scavenging of F atoms occurs and the etching rate of the resist decreases. For these reasons, in order to suppress the occurrence of striations, it is important to reduce the F atom number density by capturing it with I or other methods to form a stable compound.

In view of the above, a compound containing H, Br, I, or Xe as an etching gas can be used as a compound that stably forms a compound by reaction with F atoms and does not significantly affect the etching mechanism itself. That's fine. Here, H is difficult to control because it reacts at high speed with F to form HF and also reacts with an organic compound. Moreover, Xe forms an exciting timer with F, its bonding force is weak, and it is expensive, so it is not practical. On the other hand, Br and I form stable compounds such as IF ₃ , IF ₅ , IF ₇ B, BrF ₃ , BrF _5, etc., and also have a function as an etchant with respect to Si. There is also no function to obstruct itself.

  Therefore, in this embodiment, the etching gas is a halogen-based gas (halogen is F, I, Br), and at least one of I and Br is 26% or less of the total amount of halogen in terms of atomic composition ratio. Fluorocarbon compound gas with the remainder being F, in particular, either one of iodinated fluorocarbon compound gas and brominated fluorocarbon compound gas, or a mixed gas thereof was used.

The iodinated fluorocarbon compound gas and the brominated fluorocarbon compound gas are C _n (Hal) _{2n + 2} (where n = 1 to 3), preferably CF ₃ I, CF ₃ Br, C ₂ F _At least one selected from ₅ I, C ₂ F ₅ Br, C ₃ F ₇ I, C ₃ F ₇ Br, C ₃ F ₆ I ₂ , C ₃ F ₆ Br ₂ , or a fluorocarbon thereof A mixed gas containing two or more selected from a compound gas and HI or Br is preferable. When the number of n exceeds 3, problems such as contamination of the chamber 11 occur during etching, which is not practical.

Also, C ₂ F ₄ Bromination fluorinated carbon compound gas such as iodinated fluorocarbon compound gas and C ₂ F ₄ Br _2, such as I ₂ can also be used, in this case, of the total amount of halogen in atomic composition ratio CF ₄ gas or the like is added and used so as to be 26% or less.

The etching gas is a mixed gas of at least one of HI and HBr and a perfluorocarbon compound (C _n (Hal) _2n (where n = 1 to 3)) gas such as tetrafluoroethylene. Alternatively, a mixed gas of CF ₃ I and a fluorocarbon compound or a mixed gas of CF ₃ Br and a fluorocarbon compound may be used as an etching gas.

  Thereby, without depending on the pressure at the time of etching of the chamber 11, the F atom number density in the plasma atmosphere is decreased, damage to the resist mask is reduced, and the occurrence of striation can be suppressed. In this case, if at least one of I and Br is contained in an atomic composition ratio exceeding 26% of the total amount of halogen, there are problems such as a decrease in etching rate and inability to perform etching in a desired shape.

  Further, it is preferable to add a small amount of oxygen to the fluorocarbon compound gas in order to prevent the etched holes and trenches from being filled by adjusting the amount of reaction product deposited by etching. .

  In this case, the amount of oxygen added is set in the range of 3 to 15%, preferably 3 to 10%, more preferably 4 to 7% of the total flow rate of the gas introduced into the chamber 11. If it is less than 3%, the above effect cannot be achieved, and the amount of deposition cannot be adjusted. On the other hand, if it exceeds 15%, the ArF resist is damaged and etched.

In Example 1, SiO ₂ was used as an interlayer insulating film, and a film having a thickness of 1000 nm was formed on a processing substrate using a spin coater. Then, a resist material was applied onto the interlayer insulating film by a spin coater, and predetermined patterning was performed by an ArF photolithography method to form a resist mask. In this case, UV-6 for vacuum ultraviolet light was used as the resist material, and the thickness was 500 nm.

Next, using the NLD plasma etching apparatus 1 shown in FIG. 1, Ar and etching gas C ₃ F ₇ I were introduced into the vacuum chamber 11 under an operating pressure of 2.67 Pa. The interlayer insulating film was etched to form holes. In this case, the flow rate of Ar was set to 230 sccm, the flow rate of C ₃ F ₇ I was set to 50 sccm, and the flow rate of oxygen was set to 20 sccm. The output of the high frequency power source 19 connected to the plasma generating high frequency antenna coil 18 was set to 1 KW, the output of the high frequency power source 22 connected to the substrate electrode 21 was set to 0.3 KW, and the substrate set temperature was 10 ° C.
(Comparative Example 1)

In the first comparative example, an interlayer insulating film and a resist mask are formed under the same conditions as in the first embodiment, and the interlayer insulating film is etched under the same conditions as in the first embodiment using the NLD etching apparatus 1 shown in FIG. did. In this case, C ₃ F ₈ was used instead of C ₃ F ₇ I as an etching gas.

  3 and 4 are SEM photographs when the interlayer insulating film is etched under the conditions of Example 1 and Comparative Example 1. FIG. According to this, in Comparative Example 1, it was confirmed that edge roughening occurred in the edge portion of the patterned region of the resist mask by etching, and striations occurred in the holes (FIG. 4B). In contrast, in Example 1, it can be seen that edge roughness at the edge portion is suppressed, and the occurrence of striation is suppressed (see FIGS. 3B and 3C). .

  The interlayer insulating film and the resist mask were formed under the same conditions as in the first embodiment, and the interlayer insulating film was etched under the same conditions as in the first embodiment using the etching apparatus 1 shown in FIG. The pressure was set at 0.67 Pa. In this case, the etching rate was slightly increased, and the occurrence of striation could be suppressed. Moreover, the same result was obtained even when Br was used instead of I.

By the way, in the NLD etching apparatus, a weak magnetic field can be applied and an efficient NLD plasma can be formed at 1 Pa or less. However, at 1 Pa or more, the mean free process of electrons becomes short, and it does not become an NLD plasma. Will be formed. Accordingly, in the first embodiment, the NLD etching apparatus 1 is used. However, since it is 1 Pa or more, the effect of the magnetic field is lost, and the same plasma as the magnetic field zero is formed. For this reason, it becomes the same as what formed ICP plasma, and the effect of this invention is not dependent on an etching apparatus structure, but is dependent on plasma density and gas composition. As a result, it is apparent in principle that a similar effect can be obtained if an interlayer insulating film covered with an ArF resist mask is formed with plasma having a plasma density of 10 ¹⁰ to 10 ¹¹ cm ⁻³ .

The figure which shows schematically the etching apparatus which enforces the etching method of the interlayer insulation film of this invention. The figure explaining roughly generation | occurrence | production of striations. (A) thru | or (c) are the SEM photographs when an interlayer insulation film is etched by Example 1. FIG. (A) thru | or (c) are the SEM photographs when an interlayer insulation film is etched by the comparative example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Etching apparatus 11 Chamber 11a Plasma generation chamber 11b Substrate electrode chamber 31 Resist mask 32 Edge part 33 Edge roughening 34 Interlayer insulation film 35 Hole, trench 36 Striation S Treated substrate

Claims (7)

Dry etching of an interlayer insulating film that finely processes holes and trenches by dry etching an interlayer insulating film covered with a resist mask formed using ArF photolithography in a plasma atmosphere while introducing a predetermined etching gas In the method, the etching gas is a halogen-based gas (halogen is F, I, Br), and at least one of I and Br is an atomic composition ratio of 26% or less of the total amount of halogen, and the rest is F. A fluorocarbon compound gas , except that a fluorocarbon compound gas excluding CF ₃ Br, C ₂ F ₅ Br, C ₃ F ₇ Br, and C ₃ F ₆ Br ₂ is used. Insulating film dry etching method. The fluorocarbon compound gas, the gas iodinated fluorocarbon compound and the _{CF 3 Br, C 2 F 5} Br, C 3 F 7 Br, and _C 3 _F brominated fluorocarbon compound gas excluding 6 Br ₂ 2. The method of dry etching an interlayer insulating film according to claim 1, wherein any one of the above or a mixed gas thereof is used. The iodinated fluorocarbon compound gas is at least one selected from CF ₃ I, C ₂ F ₅ I, C ₃ F ₇ I, and C ₃ F ₆ I ₂ , or the iodinated fluorocarbon compound gas 3. The method of dry etching an interlayer insulating film according to claim 2, wherein the mixed gas contains two or more selected from HI and HBr. The etching gas, CF ₄ and _{C 2 F} 4 _I 2 or _C 2 _F 4 dry etching method of the interlayer insulating film according to claim 1, characterized in that a mixed gas of Br _2. The etching gas, the dry etching method according to claim 1 Symbol placement of the interlayer insulating film, characterized in that a mixed gas of HI and perfluorocarbon compounds. The etching gas, CF ₃ I and the dry etching method according to claim 1 Symbol placement of the interlayer insulating film to be characterized is a mixed gas of perfluorocarbon compound. The etching gas, dry the interlayer insulating film according to any one of claims 1 to 6, characterized in that the addition of oxygen in the range from 3 to 15% of the total flow rate of the etching gas Etching method.