WO2009123038A1 - プラズマエッチング方法 - Google Patents
プラズマエッチング方法 Download PDFInfo
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- WO2009123038A1 WO2009123038A1 PCT/JP2009/056245 JP2009056245W WO2009123038A1 WO 2009123038 A1 WO2009123038 A1 WO 2009123038A1 JP 2009056245 W JP2009056245 W JP 2009056245W WO 2009123038 A1 WO2009123038 A1 WO 2009123038A1
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- plasma etching
- etching method
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
Definitions
- the present invention relates to a plasma etching method using a processing gas containing a specific fluorinated hydrocarbon under plasma conditions.
- SiN film silicon nitride film covering a silicon oxide film (hereinafter also referred to as “SiO 2 film”) is dry-etched. There is a process to do.
- an etching apparatus using plasma is widely used, and an etching gas that selectively etches only the SiN film at a high etching rate with respect to the SiO 2 film is required as the processing gas.
- Patent Document 1 discloses that a processing gas used in a nitride etching process for selectively etching a SiN film having a SiO 2 film or the like as a base layer by selecting a sufficiently low power bias is represented by the formula: CH p F
- An etching gas containing a compound gas represented by 4-p p represents 2 or 3, the same applies hereinafter) and an oxygen gas is described.
- the CHF 3 gas has a SiN film selectivity with respect to the SiO 2 film (SiN film etching rate / SiO 2 film etching rate) of 5 or less, CH 2 F 2 gas has a selectivity of 10 or less.
- Patent Document 2 discloses that a plasma of an etching gas is generated in a processing chamber, and an etching gas CH is used as an etching gas in a method of etching a SiN film covering a SiO 2 film formed on an object to be processed.
- a technique has been proposed in which a mixed gas of 3 F gas and O 2 gas is used, and the mixing ratio (O 2 / CH 3 F) of O 2 gas to CH 3 F gas in the mixed gas is set to 4 to 9.
- JP-A-8-059215 JP 2003-229418 A (US Publication No. 2003-0121888)
- the present invention has been made in view of the above-described prior art, and in etching a silicon nitride film that covers a silicon oxide film formed on an object to be processed, the silicon nitride film relative to the silicon oxide film is etched. It is an object of the present invention to provide a plasma etching method having high selectivity and high etching speed.
- the present inventors use a processing gas containing a specific saturated fluorinated hydrocarbon to form a silicon nitride film that covers a silicon oxide film formed on a target object.
- the present inventors have found that the selectivity of the silicon nitride film with respect to the silicon oxide film can be increased and the etching rate can be increased when the film is etched.
- the present invention has been completed.
- a plasma etching method using a processing gas under plasma conditions wherein the processing gas has the formula (1): C x H y F z (wherein x represents 3, 4 or 5, y, and z represents a positive integer and y> z.)
- a plasma etching method comprising a saturated fluorinated hydrocarbon represented by: (2) The plasma etching method according to (1), wherein the processing gas further contains oxygen gas and / or nitrogen gas.
- a silicon nitridation covering a silicon oxide film formed on a target object by using a processing gas containing a specific saturated fluorinated hydrocarbon there is provided a plasma etching method capable of increasing the selectivity of a silicon nitride film with respect to a silicon oxide film and increasing the etching speed when etching the film.
- the plasma etching method of the present invention is a plasma etching method using a processing gas under plasma conditions, wherein the processing gas is represented by the formula (1): C x H y F z (where x is 3, 4 or 5). And y and z each independently represent a positive integer and y> z.), And a saturated fluorinated hydrocarbon represented by
- the plasma etching method of the present invention uses a gas containing the saturated fluorinated hydrocarbon represented by the above formula (1) as the processing gas, the etching selectivity of the silicon nitride film to the silicon oxide film is increased and etching is performed. You can speed up.
- the selection ratio of silicon nitride film to silicon oxide film etching means (average etching speed of silicon nitride film) / (average etching speed of silicon oxide film).
- the high etching selectivity of the silicon nitride film to the silicon oxide film is also referred to as having etching selectivity with respect to the silicon oxide film. Since the saturated fluorinated hydrocarbon gas represented by the formula (1) has etching selectivity with respect to the silicon oxide film, the silicon nitride film is efficiently etched without destroying the silicon oxide film, and the etching rate is increased. It is possible to speed up.
- etching refers to a technique of etching a very highly integrated fine pattern on a target object used in a manufacturing process of a semiconductor manufacturing apparatus.
- “Plasma etching” is a process in which a high-frequency electric field is applied to a processing gas (reactive plasma gas) to cause glow discharge to separate a gas compound into chemically active ions, electrons, and radicals. Etching is performed using a chemical reaction.
- x represents 3, 4 or 5, and x is preferably 4 or 5, preferably 4 because of the good balance between selectivity to silicon nitride film and productivity (etching rate). Particularly preferred.
- y and z each independently represent a positive integer, and y> z.
- the fluorinated hydrocarbon (1) to be used has a cyclic structure even if it has a chain structure as long as it satisfies the conditions specified by x, y and z in the formula (1).
- those having a chain structure are preferable.
- fluorinated hydrocarbon (1) examples include saturated fluorinated hydrocarbons represented by the formula: C 3 H 7 F, such as 1-fluoropropane and 2-fluoropropane; Saturated fluorinated hydrocarbons represented by the formula: C 3 H 6 F 2 , such as 1,1-difluoropropane, 1,2-difluoropropane, 1,3-difluoropropane, 2,2-difluoropropane; 1,1,1-trifluoropropane, 1,1,1-trifluoropropane, 1,1,2-trifluoropropane, 1,2,2-trifluoropropane, 1,1,3-trifluoropropane, etc.
- saturated fluorinated hydrocarbons represented by the formula: C 3 H 7 F such as 1-fluoropropane and 2-fluoropropane
- Saturated fluorinated hydrocarbons represented by the formula: C 3 H 6 F 2 such as 1,1-difluoropropane, 1,2-d
- Formulas such as 1-fluoro-n-pentane, 2-fluoro-n-pentane, 3-fluoro-n-pentane, 1-fluoro-2-methyl-n-butane, 1-fluoro-2,3-dimethylpropane Saturated fluorinated hydrocarbon represented by C 5 H 11 F; 1,1-difluoro-n-pentane, 1,2-difluoro-n-pentane, 1,3-difluoro-n-pentane, 1,5-difluoro-n-pentane, 1,1-difluoro-2-methyl- saturated fluorinated hydrocarbons represented by the formula: C 5 H 10 F 2 , such as n-butane, 1,2-difluoro-2,3-dimethylpropane; 1,1,1-trifluoro-n-pentane, 1,1,2-trifluoro-n-pentane, 1,1,3-trifluoro-n-pentane
- Fluorocyclobutane (C 4 H 7 F); Cyclic saturated fluorinated hydrocarbons represented by the formula: C 4 H 6 F 2 , such as 1,1-difluorocyclobutane, 1,2-difluorocyclobutane, 1,3-difluorocyclobutane; Cyclic saturated fluorinated hydrocarbons represented by the formula: C 4 H 5 F 3 such as 1,1,2-trifluorocyclobutane, 1,1,3-trifluorocyclobutane, 1,2,3-trifluorocyclobutane, etc. ;
- Fluorocyclopentane (C 5 H 9 F);
- a cyclic saturated fluorinated hydrocarbon represented by the formula: C 5 H 8 F 2 such as 1,1-difluorocyclopentane, 1,2-difluorocyclopentane, 1,3-difluorocyclopentane;
- Cyclic saturated fluorine represented by the formula: C 5 H 7 F 3 such as 1,1,2-trifluorocyclopentane, 1,1,3-trifluorocyclopentane, 1,2,3-trifluorocyclopentane, etc.
- Cyclic saturated fluorinated hydrocarbons of the formula: C 5 H 6 F 4 , such as pentane; Fluorocyclohexane (C 6 H 11 F); Cyclic saturated fluorinated hydrocarbons represented by the formula: C 6 H 10 F 2 , such as 1,1-difluorocyclohexane, 1,3-difluorocyclohexane, 1,4-difluorocyclohexane; Cyclic saturated fluorinated hydrocarbons represented by the formula: C 6 H 9 F 3 such as 1,1,2-trifluorocyclohexane, 1,1,3-trifluorocyclohexane, 1,1,4-trifluorocyclohexane ;
- fluorinated hydrocarbons (1) can be used singly or in combination of two or more, but are preferably used singly because the effects of the present invention are more prominent.
- fluorinated hydrocarbons (1) are known substances, and can be produced and obtained by a conventionally known method. For example, it can be obtained by a method described in Journal of the American Chemical Society (1942), 64, 2289-92, Journal of Industrial and Engineering Chemistry (1947), 39, 418-20, and the like. Further, a commercially available product can be used as it is or after purification as desired.
- the fluorinated hydrocarbon (1) is filled in an arbitrary vessel, for example, a vessel such as a cylinder like the conventional semiconductor gas, and used for plasma etching described later.
- the purity of the saturated fluorinated hydrocarbon (1) is preferably 99% by volume or more, more preferably 99.9% by volume or more, and particularly preferably 99.98% by volume or more. When the purity is in the above range, the effect of the present invention is further improved. In addition, if the purity of the fluorinated hydrocarbon (1) is too low, the gas purity (content of the fluorinated hydrocarbon (1)) may be biased in the gas-filled container. Specifically, the gas purity may be greatly different between the initial use stage and the stage where the remaining amount is low.
- the above “content of fluorinated hydrocarbon (1)” is a volume-based purity derived from a weight-based percentage (%) measured by gas chromatography analysis by the internal standard substance method.
- the etching gas is prepared by appropriately mixing other gases such as oxygen gas and nitrogen gas into the fluorinated hydrocarbon (1).
- gases such as oxygen gas and nitrogen gas
- impurities in the fluorinated hydrocarbon (1) there are moisture derived from air, nitrogen gas in production equipment, solvents used during production, highly hygroscopic salts, alkalis, and the like. If nitrogen gas, oxygen gas, or the like is present in the fluorinated hydrocarbon filled in the container, it is necessary to adjust the mixed gas amount in consideration of the amount. This is because nitrogen gas, oxygen gas, moisture, and the like dissociate in the plasma reactor and generate various free radicals (etching species), greatly affecting the plasma reaction of the fluorinated hydrocarbon (1). .
- the amount of nitrogen gas and oxygen gas contained as the remaining trace gas in the fluorinated hydrocarbon (1) is 200 ppm by volume with respect to the total amount of the fluorinated hydrocarbon (1) gas as the total amount of both. Or less, more preferably 150 ppm by volume or less, and particularly preferably 100 ppm by volume or less.
- the water content is preferably 30 ppm by weight or less, more preferably 20 ppm by weight or less, and particularly preferably 10 ppm by weight or less.
- total amount of nitrogen gas and oxygen gas is the total content (ppm) of nitrogen gas and oxygen gas based on volume measured by gas chromatography analysis using the absolute calibration curve method. Note that these volume standards can also be referred to as molar standards.
- the “water content” is usually a water content (ppm) based on weight measured by the Karl Fischer method.
- the processing gas used in the present invention preferably further contains oxygen gas and / or nitrogen gas in addition to the fluorinated hydrocarbon (1).
- oxygen gas and / or nitrogen gas is used in combination to prevent etching stop (etching stop) that may be caused by the deposition of reactants on the bottom of the hole.
- the ratio can be greatly increased.
- selectivity of SiN film to a SiO 2 film is at least 10 or more, preferably 20 or more.
- the use ratio of oxygen gas and nitrogen gas is preferably 0.1 to 50 in terms of the total volume ratio of oxygen gas, nitrogen gas, or oxygen gas and nitrogen gas to fluorinated hydrocarbon (1) gas. 0.5 to 30 is more preferable.
- the processing gas further contains at least one group 18 gas selected from the group consisting of helium, argon, neon, krypton, and xenon.
- group 18 gas selected from the group consisting of helium, argon, neon, krypton, and xenon.
- the use ratio of the group 18 gas is preferably 0 to 100, more preferably 0 to 20 in terms of volume ratio to the fluorinated hydrocarbon (1) gas.
- the introduction rate of the processing gas is proportional to the use ratio of each component.
- the fluorinated hydrocarbon (1) gas is 8 ⁇ 10 ⁇ 3 to 5 ⁇ 10 ⁇ 2 Pa ⁇ m 3 / sec
- the oxygen gas is 8 ⁇ . 10 ⁇ 2 to 5 ⁇ 10 ⁇ 1 Pa ⁇ m 3 / sec
- the group 18 gas may be 8 ⁇ 10 ⁇ 2 to 5 ⁇ 10 ⁇ 1 Pa ⁇ m 3 / sec, and the like.
- the pressure in the processing chamber into which the processing gas is introduced is usually 0.0013 to 1300 Pa, preferably 0.13 to 13 Pa.
- a plasma generator generates a plasma by generating a glow discharge by applying a high-frequency electric field to the fluorinated hydrocarbon (1) gas (reactive plasma gas) in the processing chamber.
- plasma generators examples include helicon wave method, high frequency induction method, parallel plate type, magnetron method, and microwave method. However, since plasma generation in a high density region is easy, helicon wave method, high frequency induction. The apparatus of a system and a microwave system is used suitably.
- the plasma density is not particularly limited. From the viewpoint of better expressing the effects of the present invention, etching is performed in a high-density plasma atmosphere with a plasma density of preferably 10 11 ions / cm 3 or more, more preferably 10 12 to 10 13 ions / cm 3 . Is desirable.
- the temperature reached by the substrate to be processed during etching is not particularly limited, but is preferably in the range of 0 to 300 ° C., more preferably 0 to 100 ° C., and still more preferably 20 to 80 ° C.
- the temperature of the substrate may or may not be controlled by cooling or the like.
- the time for the etching process is generally 5 to 10 minutes. However, since the processing gas used in the present invention can be etched at a high speed, the productivity can be improved in 2 to 5 minutes.
- the plasma etching method of the present invention is a method of generating a plasma of an etching gas in a processing chamber and etching a predetermined portion on an object to be processed disposed therein, which is a fluorinated hydrocarbon (
- the process gas (etching gas) containing 1) is used, but a method of selectively plasma etching the silicon nitride film is preferable, and the silicon nitride film is selectively plasma etched with respect to the silicon oxide film. More preferably, it is a method.
- etching the silicon nitride film under the above-described etching conditions it is possible to obtain a selectivity ratio of the silicon nitride film to the silicon oxide film of at least 10 or more, and in many cases, a selectivity ratio of 20 or more. While avoiding the stop, a remarkably high selection ratio can be obtained as compared with the conventional case. Therefore, even if the silicon oxide film constituting the device is made thinner, it is possible to prevent the silicon oxide film from escaping (SiO 2 film break) while etching the silicon nitride film, and to etch only the silicon nitride film reliably. Thus, a device having excellent electrical performance can be manufactured.
- a mask pattern having an opening in a predetermined region on an ONO film (silicon oxide film-silicon nitride film-silicon oxide film) is formed, and at least the upper silicon After etching the opening of the mask pattern so as to remove the oxide film, the silicon nitride film exposed in the opening is selectively etched, or (b) in the process after opening the contact hole,
- a thin silicon nitride film (for example, 10 to 20 nm thick) is formed on the side wall (inner wall) of the opened contact hole, and then silicon at the bottom of the contact hole is formed. This can be applied to the case where the nitride film is removed by etching.
- the content of the fluorinated hydrocarbon (1) in the processing gas was determined by a gas chromatography (GC) method.
- the GC measurement conditions are as follows.
- ⁇ Device HP6890, manufactured by Hewlett-Packard Company Column: NEUTRA BOND-1, Length 60 m / ID 250 ⁇ m / film 1.50 ⁇ m ⁇ Detector: FID ⁇ Injection temperature: 150 °C ⁇ Detector temperature: 250 °C
- Carrier gas Nitrogen gas (23.2 mL / min) Make-up gas: nitrogen gas (30 mL / min), hydrogen gas (50 mL / min), air (400 mL / min) ⁇ Split ratio: 137/1 ⁇ Temperature increase program: (1) Hold at 40 ° C for 20 minutes, (2) Increase temperature at 40 ° C / min, (3) Hold at 250 ° C for 14.75 minutes
- each wafer was separately etched by the etching method of the present invention. Then, the etching rates of the SiN film and the SiO 2 film were measured, and the selection ratio (SiN film / SiO 2 film) was obtained from the ratio of the etching speed of the SiN film to the SiO 2 film based on these measurement results. 2,2-Difluoro-n-butane was used as the fluorinated hydrocarbon (1).
- a wafer with a SiN film formed on the surface and a wafer with a SiO 2 film formed on the surface were set in an etching chamber of a parallel plate plasma etching apparatus, respectively, and after the system was evacuated, the following etching conditions were set.
- the etching rate of the SiN film was 64 nm / min, but the SiO 2 film was not etched at all, and an infinite selectivity ratio was obtained.
Abstract
Description
したがって、SiO2膜に対するSiN膜の選択性が高く、しかも速いエッチング速度でプラズマエッチングを行うことができるエッチングガスの開発が求められている。
(1)プラズマ条件下において処理ガスを用いるプラズマエッチング方法であって、前記処理ガスが、式(1):CxHyFz(式中、xは3、4または5を表し、y、zはそれぞれ独立して、正の整数を表し、かつ、y>zである。)で表される飽和フッ素化炭化水素を含むことを特徴とするプラズマエッチング方法。
(2)前記処理ガスが、さらに、酸素ガスおよび/または窒素ガスを含むことを特徴とする(1)に記載のプラズマエッチング方法。
(3)前記処理ガスとして、さらに、ヘリウム、アルゴン、ネオン、クリプトン、キセノンからなる群から選ばれる少なくとも1種を含むガスを用いることを特徴とする(1)または(2)に記載のプラズマエッチング方法。
(4)シリコン窒化膜をエッチングするものである(1)~(3)のいずれかに記載のプラズマエッチング方法。
(5)シリコン酸化膜に対してシリコン窒化膜を選択的にエッチングするものである(1)~(3)のいずれかに記載のプラズマエッチング方法。
本発明のプラズマエッチング方法は、プラズマ条件下において処理ガスを用いるプラズマエッチング方法であって、前記処理ガスが、式(1):CxHyFz(式中、xは3、4または5を表し、y、zはそれぞれ独立して、正の整数を表し、かつ、y>zである。)で表される飽和フッ素化炭化水素を含むことを特徴とする
前記式(1)で表される飽和フッ素化炭化水素ガスは、シリコン酸化膜に対してエッチング選択性を有するため、シリコン酸化膜を破壊することなくシリコン窒化膜を効率よくエッチングし、エッチング速度を速めることが可能である。
y、zはそれぞれ独立して、正の整数を表し、かつ、y>zである。
1,1-ジフルオロプロパン、1,2-ジフルオロプロパン、1,3-ジフルオロプロパン、2,2-ジフルオロプロパン等の、式:C3H6F2で表される飽和フッ素化炭化水素;
1,1,1-トリフルオロプロパン、1,1,1-トリフルオロプロパン、1,1,2-トリフルオロプロパン、1,2,2-トリフルオロプロパン、1,1,3-トリフルオロプロパン等の、式:C3H5F3で表される飽和フッ素化炭化水素;
1-フルオロ-n-ブタン、1,1-ジフルオロ-n-ブタン等の、式:C4H9Fで表される飽和フッ素化炭化水素;
1,1,1-トリフルオロ-n-ブタン、1,1,1-トリフルオロ-2-メチルプロパン、2,2,2-トリフルオロメチルプロパン、1,1,2-トリフルオロ-n-ブタン、1,1,3-トリフルオロ-n-ブタン、1,1,4-トリフルオロ-n-ブタン等の、式:C4H7F3で表される飽和フッ素化炭化水素;
1,1-ジフルオロ-n-ペンタン、1,2-ジフルオロ-n-ペンタン、1,3-ジフルオロ-n-ペンタン、1,5-ジフルオロ-n-ペンタン、1,1-ジフルオロ-2-メチル-n-ブタン、1,2-ジフルオロ-2,3-ジメチルプロパン等の、式:C5H10F2で表される飽和フッ素化炭化水素;
1,1,1-トリフルオロ-n-ペンタン、1,1,2-トリフルオロ-n-ペンタン、1,1,3-トリフルオロ-n-ペンタン、1,1,5-トリフルオロ-n-ペンタン、1,1,1-トリフルオロ-2-メチル-n-ブタン、1,1,2-トリフルオロ-2,3-ジメチルプロパン、2-トリフルオロメチル-n-ブタン等の、式:C5H9F3で表される飽和フッ素化炭化水素;
1,1,1,2,2-ペンタフルオロ-n-ペンタン、1,1,2,2,2-ペンタフルオロ-n-ペンタン、1,1,1,2,3-ペンタフルオロ-n-ペンタン、1,1,3,5,5-ペンタフルオロ-n-ペンタン、1,1,1,4,4-ペンタフルオロ-2-メチル-n-ブタン、1,1,1,2,3-テトラフルオロ-2,3-ジメチルプロパン、1,5-ジフルオロ-2-トリフルオロメチル-n-ブタン等の、式:C5H7F5で表される飽和フッ素化炭化水素;
1,1-ジフルオロシクロブタン、1,2-ジフルオロシクロブタン、1,3-ジフルオロシクロブタン等の、式:C4H6F2で表される環状飽和フッ素化炭化水素;
1,1,2-トリフルオロシクロブタン、1,1,3-トリフルオロシクロブタン、1,2,3-トリフルオロシクロブタン等の、式:C4H5F3で表される環状飽和フッ素化炭化水素;
1,1-ジフルオロシクロペンタン、1,2-ジフルオロシクロペンタン、1,3-ジフルオロシクロペンタン等の、式:C5H8F2で表される環状飽和フッ素化炭化水素;
1,1,2-トリフルロシクロペンタン、1,1,3-トリフルオロシクロペンタン、1,2,3-トリフルオロシクロペンタン等の、式:C5H7F3で表される環状飽和フッ素化炭化水素;
1,1,2,2-テトラフルオロシクロペンタン、1,1,2,3-テトラフルオロシクロペンタン、1,2,2,3-テトラフルオロシクロペンタン、1,2,3,4-テトラフルオロシクロペンタン等の、式:C5H6F4で表される環状飽和フッ素化炭化水素;
フルオロシクロヘキサン(C6H11F);
1,1-ジフルオロシクロヘキサン、1,3-ジフルオロシクロヘキサン、1,4-ジフルオロシクロヘキサン等の、式:C6H10F2で表される環状飽和フッ素化炭化水素;
1,1,2-トリフルオロシクロヘキサン、1,1,3-トリフルオロシクロヘキサン、1,1,4-トリフルオロシクロヘキサン等の、式:C6H9F3で表される環状飽和フッ素化炭化水素;
1,1,2,2,3-ペンタフルオロシクロヘキサン、1,1,2,2,4-ペンタフルオロシクロヘキサン、1,1,2,4,4-ペンタフルオロシクロヘキサン等の、式:C6H7F5で表される環状飽和フッ素化炭化水素;等が挙げられる。
例えば、Journal of the American Chemical Society(1942),64,2289-92、Journal of Industrial and Engineering Chemistry(1947),39,418-20等に記載された方法により製造し、入手することができる。
また、市販品をそのままで、あるいは所望により精製した後に用いることもできる。
なお、上記の「フッ素化炭化水素(1)の含有量」は、内部標準物質法によるガスクロマトグラフィー分析で測定した重量基準の百分率(%)から導かれる容量基準の純度である。
ところが、フッ素化炭化水素(1)中の不純物として、空気や生産設備内の窒素ガス等、製造時に用いる溶媒、吸湿性が高い塩、アルカリ等に由来する水分がある。
容器に充填されたフッ素化炭化水素中に、窒素ガスや酸素ガス等が存在していると、その量を考慮して混合ガス量を調整する必要が生じる。それは、窒素ガスや酸素ガス、水分等は、プラズマ反応装置内で解離して、各種の遊離基(エッチング種)を発生させる、フッ素化炭化水素(1)のプラズマ反応に大きく影響するからである。
また、フッ素化炭化水素を充填した容器内に、窒素ガスや酸素ガス、水分等が存在する場合、当該容器を開封した時点と、容器内のフッ素化炭化水素の残量が少なくなった時点とで、容器から出てくるフッ素化炭化水素ガス(1)と不純物の組成に違いが生じる。
これらのことから、フッ素化炭化水素(1)中に存在する、窒素ガスや酸素ガス、水分等の量が多くなるほど、別途混合するガス量を緻密に調整しなければ、安定したプラズマ反応を、一艇条件下で得ることはできないことになる。
18族ガスの使用割合は、フッ素化炭化水素(1)ガスに対し、容量比で0~100となることが好ましく、0~20となることがより好ましい。
処理ガスが導入された処理室内の圧力は、通常0.0013~1300Pa、好ましくは0.13~13Paである。
エッチング処理の時間は、一般的には5~10分であるが、本発明に用いる処理ガスは、高速エッチングが可能なので、2~5分として生産性を向上させることができる。
・装置:ヒューレットパッカード社製、HP6890
・カラム:NEUTRA BOND-1、Length 60m/ID 250μm/film 1.50μm
・検出器:FID
・インジェクション温度:150℃
・ディテクター温度:250℃
・キャリアーガス:窒素ガス(23.2mL/分)
・メイクアップガス:窒素ガス(30mL/分)、水素ガス(50mL/分)、空気(400mL/分)
・スプリット比:137/1
・昇温プログラム:(1)40℃で20分保持、(2)40℃/分で昇温、(3)250℃で14.75分保持
フッ素化炭化水素(1)として、2,2-ジフルオロ-n-ブタンを用いた。
混合ガスの圧力:75mTorr(10Pa)
上部電極の高周波電源の電力:100W
下部電極の高周波電源の電力:100W
上部電極と下部電極の間隔:50mm
ガスの流量:
Arガス=1.69×10-1Pa・m3/sec
O2ガス=1.69×10-1Pa・m3/sec
フッ素化炭化水素ガス=3.38×10-2Pa・m3/sec
(流量比:Ar/O2/フッ素化炭化水素=100/100/20)
電極温度:20℃
フッ素化炭化水素としてCH3Fガスを用いた以外は実施例と同じエッチング条件下でエッチングを行ったところ、SiN膜のエッチング速度56nm/min、SiO2膜のエッチング速度2nm/min、選択比28という結果を得た。
Claims (5)
- プラズマ条件下において処理ガスを用いるプラズマエッチング方法であって、前記処理ガスが、式(1):CxHyFz(式中、xは3、4または5を表し、y、zはそれぞれ独立して、正の整数を表し、かつ、y>zである。)で表される飽和フッ素化炭化水素を含むことを特徴とするプラズマエッチング方法。
- 前記処理ガスが、さらに、酸素ガスおよび/または窒素ガスを含むことを特徴とする請求項1に記載のプラズマエッチング方法。
- 前記処理ガスとして、さらに、ヘリウム、アルゴン、ネオン、クリプトン、キセノンからなる群から選ばれる少なくとも1種を含むガスを用いることを特徴とする請求項1または2に記載のプラズマエッチング方法。
- シリコン窒化膜をエッチングするものである請求項1~3のいずれかに記載のプラズマエッチング方法。
- シリコン酸化膜に対してシリコン窒化膜を選択的にエッチングするものである請求項1~3のいずれかに記載のプラズマエッチング方法。
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JP5494475B2 (ja) | 2014-05-14 |
JPWO2009123038A1 (ja) | 2011-07-28 |
TWI453818B (zh) | 2014-09-21 |
US20110068086A1 (en) | 2011-03-24 |
CN101983417A (zh) | 2011-03-02 |
KR20110002017A (ko) | 2011-01-06 |
CN101983417B (zh) | 2013-04-24 |
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